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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 <S**2> =   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 <S**2> =   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 <S**2> =   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 <S**2> =   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: 1,468

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: 1,468

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...