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prasanta13

Member

Registered: 2018-12-30

Posts: 39

TD-DFT transition probabilities from ORCA output

Dear Prof Tian,
I have performed vertical excitation using ORCA (default setting) with RSH/def2-TZVP.
The output is this, (only printing interesting texts)
STATE 1: E= 0.085477 au 2.326 eV 18760.0 cm**-1 = 0.000000
139a -> 141a : 0.380347 (c= -0.61672301)
139a -> 142a : 0.021636 (c= -0.14709245)
139a -> 144a : 0.029537 (c= 0.17186373)
140a -> 141a : 0.493712 (c= -0.70264618)
140a -> 142a : 0.021983 (c= -0.14826775)
140a -> 144a : 0.030323 (c= 0.17413609)

STATE 2: E= 0.085954 au 2.339 eV 18864.8 cm**-1 = 0.000000
139a -> 141a : 0.493490 (c= 0.70248856)
139a -> 142a : 0.022278 (c= -0.14925782)
139a -> 144a : 0.027986 (c= 0.16728926)
140a -> 141a : 0.380403 (c= -0.61676836)
140a -> 142a : 0.021947 (c= 0.14814422)
140a -> 144a : 0.027699 (c= -0.16642982)

STATE 3: E= 0.132745 au 3.612 eV 29134.1 cm**-1 = 0.000000
139a -> 142a : 0.123433 (c= 0.35133024)
139a -> 143a : 0.221706 (c= -0.47085677)
139a -> 144a : 0.117215 (c= 0.34236621)
139a -> 146a : 0.039887 (c= -0.19971670)
140a -> 142a : 0.072587 (c= -0.26941893)
140a -> 143a : 0.269701 (c= 0.51932752)
140a -> 144a : 0.061824 (c= -0.24864433)
140a -> 146a : 0.039400 (c= 0.19849355)

STATE 4: E= 0.133335 au 3.628 eV 29263.6 cm**-1 = 0.000000
137a -> 145a : 0.011128 (c= 0.10548751)
139a -> 142a : 0.086160 (c= 0.29353050)
139a -> 143a : 0.212033 (c= 0.46047060)
139a -> 144a : 0.140644 (c= 0.37502547)
140a -> 142a : 0.142376 (c= 0.37732800)
140a -> 143a : 0.156057 (c= 0.39504032)
140a -> 144a : 0.211858 (c= 0.46028051)

When I try to calculate the transition probabilities, it doesn't give back 100%. The system is a closed shell. Any suggestion? or can it be done in Multiwfn? I tried to plot the Uv-vis spectra and see the transitions by this.
Multiwfn sp.out > 11 > 3 > 15 > 0 > 533.04910
What I get,
Sum of absolute values of all transitions: 41.19493
The individual terms are ranked by magnitude of contribution:
#Transition Contribution %
2 36.69845 89.085
1 4.34905 10.557
3 0.12731 0.309
7 0.01532 0.037
4 0.00242 0.006
8 0.00215 0.005
6 0.00015 0.000
5 0.00007 0.000
9 0.00000 0.000
10 0.00000 0.000

How does it calculate the transition percentage?

sobereva

Tian Lu (Multiwfn developer)

From: Beijing

Registered: 2017-09-11

Posts: 1,773

Website

Re: TD-DFT transition probabilities from ORCA output

Please search "ORCA users" in Section 3.21.A of Multiwfn manual. You need to use "tprint 1E-8" to print more configurations.

prasanta13

Member

Registered: 2018-12-30

Posts: 39

Re: TD-DFT transition probabilities from ORCA output

Thank you, Professor Tian. I get that part. Can you please tell me what the following means?
139a -> 141a : 0.380347 (c= -0.61672301)
orb pairs config coeff ??
I get orbital pairs, but the next two numbers bothers me. What are these?

sobereva

Tian Lu (Multiwfn developer)

From: Beijing

Registered: 2017-09-11

Posts: 1,773

Website

Re: TD-DFT transition probabilities from ORCA output

0.380347 is contribution of this configuration (38.03%) to excitation, which corresponds to 100*(-0.61672301)^2

prasanta13

Member

Registered: 2018-12-30

Posts: 39

Re: TD-DFT transition probabilities from ORCA output

Thank You Prof. Tian...