Sets the parameters for the HDCPT2 model:
This calculation type keyword computes force constants and the resulting vibrational frequencies. Intensities are also computed. By default, the force constants are determined analytically if possible (for AM1, PM3, PM3MM, PM6, PDDG, RHF, UHF, MP2, CIS, all DFT methods and CASSCF), by single numerical differentiation for methods for which only first derivatives are available (MP3, MP4(SDQ), CID, CISD, CCD, CCSD, BD and QCISD), and by double numerical differentiation for those methods for which only energies are available.
Vibrational frequencies are computed by determining the second derivatives of the energy with respect to the Cartesian nuclear coordinates and then transforming to mass-weighted coordinates.This transformation is only valid at a stationary point!Thus, it ismeaninglessto compute frequencies at any geometry other than a stationary point for the method used for frequency determination.
For example, computing 6-311G(d) frequencies at a 6-31G(d) optimized geometry produces meaningless results. It is also incorrect to compute frequencies for a correlated method using frozen core at a structure optimized with all electrons correlated, or vice-versa. The recommended practice is to compute frequencies following a previous geometry optimization using the same method. This may be accomplished automatically by specifying bothOptandFreqwithin the route section for a job.
Note also that the CPHF (coupled perturbed SCF) method used in determining analytic frequencies is not physically meaningful if a lower energy wavefunction of the same spin multiplicity exists. Use theStablekeyword to test the stability of Hartree-Fock and DFT wavefunctions.
Additional related properties may also be computed during frequency calculations, including the following:
When frequencies are done analytically, polarizabilities are also computed automatically; when numerical differentiation is required (or requested withFreq=Numer), polarizabilities must be explicitly requested using thePolarkeyword (e.g.,CCSD Freq Polar).
TheVCDoption may be used to compute the vibrational circular dichroism (VCD) intensities in addition to the normal frequency analysis at the Hartree-Fock and DFT levels[Cheeseman96a].
TheROAoption computes analytic Raman optical activity intensities[Helgaker94,Dukor00,Ruud02a,Barron04,Thorvaldsen08,Cheeseman11a].
Pre-resonance Raman intensities may be computed by specifying one of the Raman options, and also includingCPHF=RdFreqwithin the route and specifying the desired frequency in the input file (see the examples for additional information).
Frequency-dependent polarizabilities and hyperpolarizabilities may be computed by includingCPHF=RdFreqwithin the route (subject to their usual availability restrictions).
Vibrational-rotational coupling can be computed usingFreq=VibRot[Califano76,Miller80,Papousek82,Clabo88,Page88,Adamo90,Miller90,Page90,Barone03]. Numerical differentiation can also be performed along modes to compute zero-point energies, anharmonic frequencies[Califano76,Miller80,Papousek82,Clabo88,Page88,Miller90,Page90,Barone04,Barone05], and anharmonic vibrational-rotational couplings ifAnharmonicis also specified[Adamo90,Barone94,Minichino94,Barone95,Barone03]. This option is only available for methods with analytic second derivatives: Hartree-Fock, DFT, CIS and MP2. Full anharmonic IR intensities are computed[Bloino12]. The DCPT2[Kuhler96,Bloino12a]and HDCPT2[Bloino12a]methods support resonance-free computations of anharmonic frequencies and partition functions. Vibronic computations include ECD[Barone12].
There are several options for performing an analysis for an electronic excitation using the Franck-Condon and/or Herzberg-Teller methods (see below).
The keywordOpt=CalcAllrequests that analytic second derivatives be done at every point in a geometry optimization. Once the requested optimization has completed all the information necessary for a frequency analysis is available. Therefore, the frequency analysis is performed and the results of the calculation are archived as a frequency job.
These sections specify the format of the input sections for theSelectNormalModes,SelectAnharmonicModesandSelectFranckCondonModesoptions. The modes to select are specified in a separate blank-line terminated input section. The initial mode list is always empty.
Integers and integer ranges without a keyword are interpreted as mode numbers, although the [not]modekeywords may be used. The keywordsatomsandnotatomscan be used to define an atom list whose modes should be included/excluded (respectively). Atoms can also be specified by ONIOM layer via the [not]layerkeywords, which accept these values:realfor the real system,modelfor the model system in a 2-layer ONIOM,middlefor the middle layer in a 3-layer ONIOM, andsmallfor the model layer of a 3-layer ONIOM. Atoms may be similarly included/excluded by residue withresidueandnotresidue, which accept lists of residue names or numbers. Both keyword sets function as shorthand forms for atom lists.
Here are some examples:
2-5Includes modes 2 through 5.atoms=OIncludes modes involving oxygen atoms.1-20 atoms=FeIncludes modes 1 through 20 and any modes involving iron atoms.layer=real notatoms=HIncludes modes for heavy atoms in low layer (subject to default threshold).
Raman
Compute Raman intensities in addition to IR intensities. This is the default for Hartree-Fock. It may be specified for DFT and MP2 calculations. For MP2, Raman intensities are produced by numerical differentiation of dipole derivatives with respect to the electric field (equivalent toNRaman).
NRaman
Compute polarizability derivatives by numerically differentiating the analytic dipole derivatives with respect to an electric field. This is the default forMP2=Raman.
NNRaman
Compute polarizability derivatives by numerically differentiating the analytic polarizability with respect to nuclear coordinates.
NoRaman
Skips the extra steps required to compute the Raman intensities during Hartree-Fock analytic frequency calculations, saving 10-30% in CPU time.
VCD
Compute the vibrational circular dichroism (VCD) intensities in addition to the normal frequency analysis. This option is valid for Hartree-Fock and DFT methods. This option also computes optical rotations (seePolar=OptRot).
ROA
Compute dynamic analytic Raman optical activity intensities using GIAOs[Cheeseman11a]. This procedure requires one or more incident light frequencies to be supplied in the input to be used in the electromagnetic perturbations (CPHF=RdFreqis the default withFreq=ROA). This option is valid for Hartree-Fock and DFT methods.NNROAsays to use the numerical ROA method from Gaussian 03; this is useful only for reproducing the results of prior calculations.
VibRot
Analyze vibrational-rotational coupling.
Anharmonic
Do numerical differentiation along modes to compute zero-point energies, anharmonic frequencies, and anharmonic vibrational-rotational couplings ifVibRotis also specified. This option is only available for methods with analytic second derivatives: Hartree-Fock, DFT, CIS and MP2. This output includes IR intensities.
ReadAnharm
Read an input section with additional parameters for the vibrational-rotational coupling and/or anharmonic vibrational analysis (VibRotorAnharmonicoptions). Available input options are documented below following the examples.
SelectAnharmonicModes
Read an input section selecting which modes are used for differentiation in anharmonic analysis. The format of this input section is discussed above.SelAnharmonicModesis a synonym for this option.
Projected
For a point on a mass-weighted reaction path (IRC), compute the projected frequencies for vibrations perpendicular to the path. For the projection, the gradient is used to compute the tangent to the path. Note that this computation is very sensitive to the accuracy of the structure and the path[Baboul97]. Accordingly, the geometry should be specified to at least 5 significant digits. This computation is not meaningful at a minimum.
HinderedRotor
Requests the identification of internal rotation modes during the harmonic vibrational analysis[McClurg97,Ayala98,McClurg99]. If any modes are identified as internal rotation, hindered or free, the thermodynamic functions are corrected. The identification of the rotating groups is made possible by the use of redundant internal coordinates. Because some structures, such as transition states, may have a specific bonding pattern not automatically recognized, the set of redundant internal coordinates may need to be altered via theGeom=Modifykeyword. Rotations involving metals require additional input via theReadHinderedRotoroption (see below).
If the force constants are available on a previously generated checkpoint file, additional vibrational/internal rotation analyses may be performed by specifyingFreq=(ReadFC, HinderedRotor). SinceOpt=CalcAllautomatically performs a vibrational analysis on the optimized structure,Opt=(CalcAll, HinderedRotor)may also be used.
ReadHinderedRotor
Causes an additional input section to be read containing the rotational barrier cutoff height (in kcal/mol) and optionally the periodicity, symmetry number and multiplicity for rotational modes. Rotations with barrier heights larger than the cutoff value will be automatically frozen. If the periodicity value is negative, then the corresponding rotor is also frozen. You must provide the periodicity, symmetry and spin multiplicity for all rotatable bonds contain metals. The input section is terminated with a blank line, and has the following format:
VMax-valueAtom1 Atom2 periodicity symmetry spinRepeated as necessary.…
The following options perform an analysis for an electronic excitation using the corresponding method; these jobs use vibrational analysis calculations for the ground state and the excited state to compute the amplitudes for electronic transitions between the two states. The vibrational information for the ground state is taken from the current job (FreqorFreq=ReadFC), and the vibrational information for the excited state is taken from a checkpoint file, whose name is provided in a separate input section (enclose the path in quotes if it contains internal spaces). The latter will be from a CI-Singles or TD-DFTFreq=SaveNormalModescalculation.
TheReadFCHToption can be added to cause additional input to be read to control these calculations (see below), and theSelFCModesoption can be used to select the modes involved. In the latter case, the excited state checkpoint file would typically have been generated withFreq=(SelectNormalModes, SaveNormalModes)with the same modes selected.
If CIS frequencies are to be used with the Herzberg-Teller or Franck-Condon-Herzberg-Teller analysis, the CIS frequencies must be done numerically (Freq=Numerrather thanFreq). This is because the transition dipole derivatives are not computed during the analytic force constant evaluation. The corresponding HF frequency calculation on the ground state, which is also required, can be done analytically as usual.
FranckCondon
Use the Franck-Condon method[Sharp64,Doktorov77,Kupka86,Zhixing89,Berger97,Peluso97,Berger98,Borrelli03,Weber03,Coutsias04,Dierksen04,Lami04,Dierksen04a,Dierksen05,Liang05,Jankowiak07,Santoro07,Santoro07a,Barone09](the implementation is described in[Santoro07,Santoro07a,Santoro08,Barone09]).FCis a synonym for this option. Transitions for ionizations can be analyzed instead of excitations. In this case, the molecule specification corresponds to the neutral form, and the additional checkpoint file named in the input section corresponds to the cation.
HerzbergTeller
Use the Herzberg-Teller method[Herzberg33,Sharp64,Small71,Orlandi73,Lin74,Santoro08](the implementation is described in[Santoro08]).HTis a synonym for this option.
FCHT
Use the Franck-Condon-Herzberg-Teller method[Santoro08].
Emission
Indicates that emission rather than absorption should be simulated for a Franck-Condon and/or Herzberg-Teller analysis. In this case, within the computation the initial state is the excited state, and the final state is the ground state (although the sources of frequency data for the ground and excited state are as described above: current job=ground state, second checkpoint file=excited state).
ReadFCHT
Read an input section containing parameters for the calculation. Available input options are documented below following the examples. This input section precedes that forReadAnharmonif both are present.
SelectFranckCondonModes
Read an input section selecting which modes are used for differentiation in Franck-Condon analysis. The format of this input section is discussed above. This input section precedes that forSelectAnharmonicModesif both are present, and the modes are specified in the usual Gaussian order (increasing), not the order displayed in the anharmonic output.SelFCModesis a synonym for this option.
HPModes
Include the high precision format (to five figures) vibrational frequency eigenvectors in the frequency output in addition to the normal three-figure output.
InternalModes
Print modes as displacements in redundant internal coordinates.IntModesis a synonym for this option.
SaveNormalModes
Save all modes in the checkpoint file.SaveNMis a synonym for this option.NoSaveNormalModes, orNoSaveNM, is the default.
ReadNormalModes
Read saved modes from the checkpoint file.ReadNMis a synonym for this option.NoReadNormalModes, orNoReadNM, is the default.
SelectNormalModes
Read input selecting the particular modes to display.SelectNMis a synonym for this option.NoSelectNormalModes, orNoSelectNM, is the default.AllModessays to include all modes in the output. The format of this input section is discussed above. Note that this option doesnotaffect the functioning ofSaveNormalModes, which always saves all modes in the checkpoint file.
SortModes
Sort modes by ONIOM layer in the output.
ModelModes
Display only modes involving the smallest model system in an ONIOM calculation.
MiddleModes
Display only modes involving the two model systems in a 3-layer ONIOM.
PrintFrozenAtoms
By default, the zero displacements for frozen atoms are not printed in the mode output. This option requests that all atoms be listed.
NoPrintNM
Used to suppress printing of the normal mode components during a frequency calculation. The frequencies and intensities are still reported for each mode.
ModRedundant
Read-in modifications to redundant internal coordinates (i.e., for use withInternalModes). Note that the same coordinates are used for both optimization and mode analysis in anOpt Freq, for which this is the same asOpt=ModRedundant. See the discussion of theOptkeyword for details on the input format.
ReadIsotopes
This option allows you to specify alternatives to the default temperature, pressure, frequency scale factor and/or isotopes—298.15 K, 1 atmosphere, no scaling, and the most abundant isotopes (respectively). It is useful when you want to rerun an analysis using different parameters from the data in a checkpoint file.
Be aware, however, that all of these can be specified in the route section (Temperature,PressureandScalekeywords) and molecule specification (Iso=parameter), as in this example:
#TMethod/6-31G(d)JobTypeTemperature=300.0… … 0 1 C(Iso=13) …ReadIsotopesinput has the following format:
temppressure[scale]Values must be real numbers.isotope mass for atom 1isotope mass for atom 2…isotope mass for atom n
wheretemp,pressure, andscaleare the desired temperature, pressure, and an optional scale factor for frequency data when used for thermochemical analysis (the default is unscaled). The remaining lines hold the isotope masses for the various atoms in the molecule, arranged in the same order as they appeared in the molecule specification section. If integers are used to specify the atomic masses, the program will automatically use the corresponding actual exact isotopic mass (e.g., 18 specifies18O, and Gaussian uses the value 17.99916).
Analytic
This specifies that the second derivatives of the energy are to be computed analytically. This option is available only for RHF, UHF, CIS, CASSCF, MP2, and all DFT methods, and it is the default for those cases.
Numerical
This requests that the second derivatives of the energy are to be computed numerically using analytically calculated first derivatives. It can be used with any method for which gradients are available and is the default for those for which gradients but not second derivatives are available.Freq=Numercan be combined withPolar=Numerin one job step.
DoubleNumer
This requests double numerical differentiation of energies to produce force constants. It is the default and only choice for those methods for which no analytic derivatives are available.EnOnlyis a synonym forDoubleNumer.
Cubic
Requests numerical differentiation of analytic second derivatives to produce third derivatives. Applicable only to methods having analytic frequencies but no analytic third derivatives.
Step=N
Specifies the step-size for numerical differentiation to be 0.0001*N(in Angstoms unlessUnits=Bohrhas been specified). IfFreq=NumerandPolar=Numerare combined,Nalso specifies the step-size in the electric field. The default is 0.001 Å for Hartree-Fock and correlatedFreq=Numer, 0.005 Å for GVB and CASSCFFreq=Numer, and 0.01 Å forFreq=EnOnly. ForFreq=AnharmonicorFreq=VibRot, the default is 0.025 Å.
Restart
This option restarts a numerical frequency calculation after the last completed geometry. A failed numerical frequency job may be restarted from its checkpoint file by simply repeating the route section of the original job, adding theRestartoption to theFreq=Numerkeyword/option. No other input is required.
Analytic frequencies can be restarted with theRestartkeyword provided that the read-write file was named and saved from the failed job. See the description of that keyword for more information and an example.
DiagFull
Diagonalize the full (3Natoms)2force constant matrix—including the translation and rotational degrees of freedom—and report the lowest frequencies to test the numerical stability of the frequency calculation. This precedes the normal frequency analysis where these modes are projected out. Its output reports the lowest 9 modes, the upper 3 of which correspond to the 3 smallest modes in the regular frequency analysis. Under ideal conditions, the lowest 6 modes reported by this analysis will be very small in magnitude. When they are significantly non-zero, it indicates that the calculation is not perfectly converged/numerically stable. This may indicate that translations and rotations are important modes for this system, that a better integration grid is needed, that the geometry is not converged, etc. The system should be studied further in order to obtain accurate frequencies. See the examples section below for the output from this option.
DiagFullis the default;NoDiagFullsays to skip this analysis.
ReadFC
Requests that the force constants from a previous frequency calculation be read from the checkpoint file, and the mode and thermochemical analysis be repeated, presumably using a different temperature, pressure, or isotopes, at minimal computational cost. Note that since the basis set is read from the checkpoint file, no general basis should be input. If theRamanoption was specified in the previous job, then do not specify it again when using this option.
TwoPoint
When computing numerical derivatives, make two displacements in each coordinate. This is the default.FourPointwill make four displacements but only works with Link 106 (Freq=Numer). Not valid withFreq=DoubleNumer.
NFreq=N
Requests that the lowestNfrequencies be solved for using Davidson diagonalization. At present, this option is only available for ONIOM(QM:MM) model chemistries.
Analytic frequencies are available for the AM1, PM3, PM3MM, PM6, PDDG, DFTB, DFTBA, HF, DFT, MP2, CIS and CASSCF methods. Numerical frequencies are available for MP3, MP4(SDQ), CID, CISD, CCD, CCSD and QCISD. Raman is available for the HF, DFT and MP2 methods. VCD and ROA are available for HF and DFT methods. Anharmonic is available for HF, DFT, MP2 and CIS methods.FreqandNMRcan now both be on the same route for HF and DFT.
Frequency Output.The basic components of the output from a frequency calculation are discussed in detail in chapter 4 ofExploring Chemistry with Electronic Structure Methods[Foresman96b].
New Gaussian users are often surprised to see that the final part frequency calculation output that looks that of a geometry optimization at the beginning of a frequency job:
GradGradGradGradGradGradGradGradGradGradGradGradGradGradGrad Berny optimization. Initialization pass.
Link 103, which performs geometry optimizations, is executed at the beginning and end of all frequency calculations. This is done so that the quadratic optimization step can be computed using the correct second derivatives. Occasionally an optimization will complete according to the normal criterion using the approximate Hessian matrix, but the step size is actually larger than the convergence criterion when the correct second derivatives are used. The next step is printed at the end of a frequency calculation so that such problems can be identified. If you think this concern is applicable, useOpt=CalcAllinstead ofFreqin the route section of the job, which will complete the optimization if the geometry is determined not to have fully converged (usually, given the full second derivative matrix near a stationary point, only one additional optimization step is needed), and will automatically perform a frequency analysis at the final structure.
Specifying#Pin the route section produces some additional output for frequency calculations. Of most importance are the polarizability and hyperpolarizability tensors (they still may be found in the archive entry in normal print-level jobs). They are presented in lower triangular and lower tetrahedral order, respectively (i.e., αxx, αxy, αyy, αxz, αyz, αzzand βxxx, βxxy, βxyy, βyyy, βxxz, βxyz, βyyz, βxzz, βyzz, βzzz), in the standard orientation:
Dipole = 2.37312183D-16 -6.66133815D-16 -9.39281319D-01 Polarizability= 7.83427191D-01 1.60008472D-15 6.80285860D+00 -3.11369582D-17 2.72397709D-16 3.62729494D+00 HyperPolar = 3.08796953D-16 -6.27350412D-14 4.17080415D-16 5.55019858D-14 -7.26773439D-01 -1.09052038D-14 -2.07727337D+01 4.49920497D-16 -1.40402516D-13 -1.10991697D+01
#Palso produces a bar-graph of the simulated spectra for small cases.
Thermochemistry analysis follows the frequency and normal mode data:
Zero-point correction= .023261 (Hartree/Particle) Thermal correction to Energy= .026094 Thermal correction to Enthalpy= .027038 Thermal correction to Gibbs Free Energy= .052698 Sum of electronic and zero-point Energies=-527.492585E0=Eelec+ZPESum of electronic and thermal Energies= -527.489751E= E0+ Evib+ Erot+EtransSum of electronic and thermal Enthalpies=-527.488807H=E+RTSum of electronic and thermal Free Energies=-527.463147G=H-TS
The raw zero-point energy correction and the thermal corrections to the total energy, enthalpy, and Gibbs free energy (all of which include the zero-point energy) are listed, followed by the corresponding corrected energy. The analysis uses the standard expressions for an ideal gas in the canonical ensemble. Details can be found in McQuarrie[McQuarrie73]and other standard statistical mechanics texts. In the output, the various quantities are labeled as follows:
E (Thermal)Contributions to the thermal energy correctionCVConstant volume molar heat capacitySEntropyQPartition function
The thermochemistry analysis treats all modes other than the free rotations and translations as harmonic vibrations. For molecules having hindered internal rotations, this can produce slight errors in the energy and heat capacity at room temperatures and can have a significant effect on the entropy. The contributions of any very low frequency vibrational modes are listed separately so that their harmonic contributions can be subtracted from the totals and their correctly computed contributions included should they be group rotations and high accuracy is required. Expressions for hindered rotational contributions to these terms can be found in Benson[Benson68]. The partition functions are also computed, with both the bottom of the vibrational well and the lowest (zero-point) vibrational state as reference.
Pre-resonance Raman.This calculation type is requested with one of theRamanoptions in combination withCPHF=RdFreq. The frequency specified for the latter should be chosen as follows:
Pre-resonance Raman results are reported as additional rows within the normal frequency tables:
Harmonic frequencies (cm**-1), IR intensities (KM/Mole), Raman scattering activities (A**4/AMU), depolarization ratios for plane and unpolarized incident light, reduced masses (AMU), force constants (mDyne/A), and normal coordinates: 1 B1 Frequencies -- 1315.8011 Red. masses -- 1.3435 Frc consts -- 1.3704 IR Inten -- 7.6649 Raman Activ -- 0.0260 Depolar (P) -- 0.7500 Depolar (U) -- 0.8571RamAct Fr= 1-- 0.0260Additional output lines begin here.Dep-P Fr= 1-- 0.7500Dep-U Fr= 1-- 0.8571RamAct Fr= 2-- 0.0023Dep-P Fr= 2-- 0.7500Dep-U Fr= 2-- 0.8571
Vibration-Rotation Coupling Output.If theVibRotoption is specified, then the harmonic vibrational-rotational analysis appears immediately after the normal thermochemistry analysis in the output, introduced by this header:
Vibro-Rotational Analysis at the Harmonic level
If anharmonic analysis is requested as well (i.e.,VibRotandAnharmonicare both specified), then the anharmonic vibrational-rotational analysis results follow the harmonic ones, introduced by the following header:
2nd order Perturbative Anharmonic Analysis
Anharmonic Frequency Calculations.Freq=Anharmonicjobs produce additional output following the normal frequency output. (It follows the vibrational-rotational coupling output if this was specified as well.) We will briefly consider the most important items.
The output displays the equilibrium geometry (i.e., the minimum on the potential energy surface), followed by the anharmonic vibrationally averaged structure at 0 K:
Internal coordinates for the Equilibrium structure (Se) Interatomic distances: 1 2 3 4 1 C 0.000000 2 O 1.206908 0.000000 3 H 1.083243 2.008999 0.000000 4 H 1.083243 2.008999 1.826598 0.000000 Interatomic angles: O2-C1-H3=122.5294 O2-C1-H4=122.5294 H3-C1-H4=114.9412 O2-H3-H4= 62.9605 Dihedral angles: H4-C1-H3-O2= 180. Internal coordinates for the vibr.aver. structure at 0K (Sz) Interatomic distances: 1 2 3 4 1 C 0.000000 2 O 1.210431 0.000000 3 H 1.097064 2.024452 0.000000 4 H 1.097064 2.024452 1.849067 0.000000 Interatomic angles: O2-C1-H3=122.57 O2-C1-H4=122.57 H3-C1-H4=114.8601 O2-H4-H3= 62.8267 Dihedral angles: H4-C1-H3-O2= 180.
Note that the bond lengths are slightly longer in the latter structure. The anharmonic zero point energy is given shortly thereafter in the output, preceded by its component terms:
ZPEharm = 6359.86859 cm-1= 18.184 Kcal/mol = 76.081 Kj/mol ZPEfund = 6135.92666 cm-1= 17.543 Kcal/mol = 73.402 KJ/mol ZPEaver = 6247.89762 cm-1= 17.864 Kcal/mol = 74.741 KJ/mol -1/4sumXii = 22.67024 cm-1= 0.065 Kcal/mol = 0.271 KJ/mol x0 = -6.63071 cm-1= -0.019 Kcal/mol = -0.079 KJ/mol ZPEtot = 6263.93715 cm-1= 17.909 Kcal/mol = 74.933 KJ/mol ZPEtot/ZPEharm = 0.98492 ZPEfund/ZPEharm= 0.96479
The anharmonic frequencies themselves appear just a bit later in this table, in the column labeledE(anharm):
Vibrational Energies and Rotational Constants (cm-1) Mode(Quanta) E(harm) E(anharm) Aa(z) Ba(x) Ca(y) Equilibrium Geometry 10.026637 1.293823 1.145922 Ground State 6359.869 6263.937 9.905085 1.288586 1.136128 Fundamental Bands (DE w.r.t. Ground State) 1(1) 3162.302 2990.777 9.727534 1.287879 1.133639 2(1) 1915.637 1884.683 9.913583 1.284564 1.128397 3(1) 1692.660 1657.100 9.955741 1.294044 1.133257 4(1) 1337.296 1315.965 6.861429 1.277085 1.137163 5(1) 3233.358 3068.112 9.809451 1.286693 1.134405 6(1) 1378.483 1355.216 12.919667 1.290780 1.130316
The harmonic frequencies are also listed for convenience.
Examining Low Lying Frequencies.The output from the full force constant matrix diagonalization (the defaultFreq=DiagFull), in which the rotational and translational degrees of freedom are retained, appears as following in the output:
Low frequencies --- -19.9673 -0.0011 -0.0010 0.0010 14.2959 25.6133 Low frequencies --- 385.4672 988.9028 1083.0692
This output is from anOpt Freqcalculation on methanol. Following that are essentially 0, the lowest modes (ignoring sign) are located at around 14, 19 and 25 wavenumbers. If we rerun the calculation using tight optimization criteria and a larger integration grid (Opt=Tight Int=UltraFine), the lowest modes become:
Low frequencies --- -7.4956 -5.4813 -2.6908 0.0003 0.0007 0.0011 Low frequencies --- 380.1699 988.1436 1081.9083
The low-lying modes are now quite small, and the lowest frequencies have moved slightly as a result.
This analysis is especially important for molecular systems having frequencies at small wavenumbers. For example, if the lowest reported frequency is around 30 and there is a low lying mode around 25 as above, then the former value is in considerable doubt (as is whether the molecular structure is even a minimum).
Rerunning a Frequency Calculation with Different Thermochemistry Parameters.The following two-step job contains an initial frequency calculation followed by a second thermochemistry analysis using a different temperature, pressure, and selection of isotopes:
%Chk=freq # HF/6-31G(d,p) Freq Test Frequencies at STPmolecule specification-Link1- %Chk=freq %NoSave # HF/6-31G(d,p) Freq(ReadIso,ReadFC) Geom=Check Test Repeat at 300 K 0,1 300.0 1.0 16 2 3 ...
Note also that thefreqchkutility may be used to rerun the thermochemical analysis from the frequency data stored in a Gaussian checkpoint file.
This input is read in a separate section. Its format changed with revision D.01. The following table gives the equivalents for the older keyword forms:
| Old Keyword | New Keyword |
|---|---|
| DaDeMin | Resonances=DaDeMin |
| DelFre | Resonances=DFreqDD |
| DelVPT | Resonances=DPT2Var |
| EnerInp | InpDEner |
| Fermi | Property=Fermi |
| InDerAJ | DataSrc=InDerAJ |
| InDerAU | DataSrc=InDerAU |
| InDerGau | DataSrc=InDerGau |
| InDerRed | DataSrc=InDerRed |
| InFreq | DataAdd=Freq |
| InGauDer | DataSrc=InGauDer |
| NoCor | DataMod=NoCor |
| NoReord | DataSrc=NMOrder=DescNoIrrep; Print=NMOrder=DescNoIrrep |
| Reduced | DataSrc=Reduced |
| Reord | DataSrc=NMOrder=Desc; Print=NMOrder=Desc |
| ScHarm | DataMod=ScHarm |
| TolCor | Tolerances=Coriolis |
| TolDE3 | Tolerances=Cubic |
| TolDE4 | Tolerances=Quartic |
| TolGra | Tolerances=Gradient |
| TolHes | Tolerances=Hessian |
| TolIne | Tolerances=Inertia |
Print=items
Control the printing of data. Items can include:
DataSrc=keyword
Select the main source of data, via one of the following keywords:
DataAdd=Freq
Replace harmonic frequencies with values given in input stream (in cm−1).
DataMod=items
Modify input data with an automatic or semi-automatic procedure. Items can include:
Tolerances=items
Modify the tolerance threshold to include/discard constants. Items are:
RedDim=items
Controls the selective treatment of a part of the complete system. Items are:
PT2Model=model
Sets the VPT2 model to use:
HDCPT2=params
Sets the parameters for the HDCPT2 model:
Resonances=params
Sets resonance thresholds and parameters for GVPT2 calculations:
The following indicates the ordering of input within this section of the Gaussian input file:
Freq=ReadAnharmkeywords and options
blank line
RedDim=Inactivedata
blank line
DataAdd=Freqdata
blank line
DataSrc=option(other thanCalcorChk) data
blank line
DataMod=SkipPT2=OptModesoptions (separated by spaces)
DataMod=SkipPT2normal modes
blank line
Resonances=Listdata
blank line
If one or more of these options are not used, then the blank line ending its subsection would be omitted.
Example Input Files
Example 1: Frequency data calculated in the current job:
%chk=example1 #p B3LYP/6-311+G(d,p) Integral=Ultrafine Freq=(Anharmonic,ReadAnharm)
Anharmonic frequencies example
0 1 C 0.0000000000 0.0000000000 0.0283020404 O 0.0000000000 0.0000000000 1.2300226532 H 0.9396636401 0.0000000000 -0.5591623468 H -0.9396636401 0.0000000000 -0.5591623468
Print=NMOrder=AscNoIrrepFreq=ReadAnharm keywords and optionsDataSrc=NMOrder=Print DataMod=SkipPT2=Modes RedDim=Inactive=1 Resonances=List=Addblank line6RedDim=Inactive (list of normal modes)blank line4 5DataMod=SkipPT2=Modes (list of normal modes)blank line2 3 3Resonances=List (list of resonances)3 3blank line
Example 2: Frequency data read from input file. It uses the checkpoint file from Example 1 to retrieve the molecular geometry and Hessian:
%oldchk=example1 %chk=example2 #p B3LYP/6-311+G(d,p) Integral=Ultrafine Freq=(ReadFC,Anharmonic,ReadAnharm) Geom=Check
Anharmonic frequencies example
0 1
Print=NMOrder=AscNoIrrepFreq=ReadAnharm keywords and optionsDataSrc=(InDerAU,NMOrder=Print) DataAdd=Freq DataMod=SkipPT2=Modes RedDim=Inactive=1 Resonances=List=Addblank line6RedDim=Inactive (list of normal modes)blank line1198.351DataAdd=Freq (list of harmonic frequencies)1259.285 1530.636 1814.590 2884.164 2941.556blank line1 1 0.054345DataSrc=InDerAU (list of force constants)2 2 0.060012 3 3 0.088662 6 6 0.327451 3 1 1 -0.010063 3 2 2 0.018871 3 3 3 -0.011382 6 3 2 0.049417 6 6 3 0.052014 1 1 1 1 0.058497 2 2 1 1 0.013491 2 2 2 2 0.048526 3 3 1 1 0.007299 3 3 2 2 0.026738 3 3 3 3 0.012838 6 6 1 1 -0.353903 6 6 2 2 -0.257164 6 6 3 3 -0.277332 x 1 3 -0.645574 x 1 4 0.567634 x 1 5 0.510907 y 2 3 -0.212852 y 2 4 -0.352650 y 2 5 -0.911225 y 3 6 -0.892797 y 4 6 0.449118 y 5 6 0.034736 z 1 2 0.528315 z 1 6 0.849048blank line4 5DataMod=SkipPT2=Modes (list of normal modes)blank line2 3 3Resonances=List (list of resonances)3 3blank line
This input is read in a separate section which can contain the following keywords:
MaxOvr=N |
Sets the maximum overtone to reach when calculating the Franck-Condon factors corresponding to transitions to single excited vibrational state. The default value is 20. |
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MaxCMB=N |
Sets the maximum overtones reached by both states involved in two-state combinations of the final state. The default value is 13. |
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MaxInt=N |
Sets the maximum number of integrals (in millions) computed for each class of transitions. The default value is 100. |
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NoIntAn |
Deactivates the use of the Sharp and Rosenstock analytic formulae to compute transition integrals to single overtones and two-state combinations. |
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NoRelI00 |
By default, spectra bounds are given with respect to the energy of the I00transition. This keyword must be given if absolute energies are given as spectrum bounds by the user. |
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SpecMin=x |
Sets the lower bound (in cm-1) of the final photoelectron spectrum. Must be a real number. The default value is -1000. |
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SpecMax=x |
Sets the upper bound (in cm-1) of the final photoelectron spectrum. Must be a real number. The default value is +8000. |
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SpecRes=x |
Sets the gap (in cm-1) between two points of the discretized spectrum. This value can greatly influence the times of computations, very low values slowing greatly the calculation, especially if HWHM is set high. Must be a real number. The default value is 8. |
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SpecHwHm=x |
Sets the Half-Width at Half-Maximum (in cm-1) of the spectral bands expressed with a Gaussian function. Must be a real number. The default value is 135. |
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DeltaSP=x |
Sets a threshold for terminating the calculation due to poor convergence. This value should be less than 1.0 (which corresponds to perfect convergence). The default is 0.0 (don’t terminate the calculation). |
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AllSpectra |
Prints in the Gaussian output the resulting spectra for each set of combinations (class) in addition to the final spectrum. This printing is deactivated by default |
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PrtMat=N |
A succession of figures to print different matrices used as a basis for integrals calculations:1for the Duschinsky matrixJ,2for the shift vectorK,3forA,4forB,5forC,6forDand7forE, whereA,B,C,D,Eare the Sharp and Rosenstock matrices. The order of the figures is not important. The default value is 0. |
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PrtInt=x |
Sets which integrals should be printed in output. The threshold is a fraction of the I00intensity. Must be a real number. The default value is 0.01. |
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DoTemp |
Enables the inclusion of temperature for the spectrum computation. By default, spectrum computation is performed at 0 K. |
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MinPop=x |
Sets the minimum population of a vibrational state to be taken into account as the starting point of a transition. The default value is 0.1. |
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InFrS0 |
Forces the program to use frequencies given by the user for the initial state. These frequencies are specified in the input after theFreq=ReadFCHToptions line. |
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InFrS1 |
Forces the program to use frequencies given by the user for the final state. These frequencies are specified in the input after theFreq=ReadFCHToptions line. |
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JDusch,JIdent |
Forces the program to use the normal Duschinsky matrix (JDusch, the default) or an identity matrix as the Duschinsky matrix (JIdent). In the latter case, rotation of the modes is not taken into account. The default value is 0. |
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SclVec |
Enables computation of a scaling vector to modify frequencies of the final states using the scaling vector of the frequencies of the initial state and the Duschinsky matrix. When this keyword, is given, user frequencies are asked for the initial state in the same way asInFrS0. |
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InpDEner=x |
Replaces the computed ΔEbetween initial and final states by a user-given one. Must be a real number. The default value is 0. |
Last update: 16 April 2014