(It is not necessary to upload input files, they can be found in the output file.)

linqiaosong
Posts: 2
Joined: 08 Feb 2020, 06:14
First name(s): Qiaosong
Last name(s): Lin
Affiliation: Wuhan University
Country: China

Last night, I calculated the phosphorescence response of the HF molecule using Dalton2019.alpha, and got the phosphorescence lifetime of the HF molecule. However, there is a question I wanna ask...The output information is following:

Code: Select all

Phosphorescence transition rate from excited state no.  1
(Triplet->singlet transition, high-temperature limit)

Transition energy:  8.737 eV
or   141.915 nm

Length gauge:
Partial rates (H_SO): X-polarization 1.45786E+05 Transition moment :  1.434E-02
Length gauge:
Partial rates (H_SO): Y-polarization  0.0000     Transition moment :   0.00
Length gauge:
Partial rates (H_SO): Z-polarization  9494.0     Transition moment :  3.660E-03

Phosphorescence - length gauge:
Oscillator strength (/2PI)     (H_SO)    7.461901E-06
Dipole strength [a.u.]         (H_SO)    2.190450E-04
Dipole strength E-40 [esu**2 cm**2]      1.415134E+01
Total transition rate          (H_SO)    5.175992E+04 s-1
Total phosphorescence lifetime (H_SO)    1.931997E-05 s
As we all known, the lifetime of phosphorescence is following the formula: lifetime(s)=1.5/(Oscillator strength * (Transition energy(cm-1))^2)
If we use the result of output file, we will find that: lifetime=1.5/((7.461901E-06)*(2*PI)*(1/(141.915E-7)^2))=6.44345082456349E-06 s, which is the 1/3 of 1.931997E-05 s. What's more, we found that this phenomenon is common. Thus, I wanna know this factor 1/3 is the bug or the feature of Dalton Program?

The input and output files are following:
Attachments
test.out
test.mol
test.dal

olav
Posts: 145
Joined: 28 Aug 2013, 06:20
First name(s): Olav
Last name(s): Vahtras

Dear Qiaosong
For transitions between non-degenerate states, the general rule for the total transition rate is to average initial states and sum over final states. In the most common picture with a T->S transition, an ensemble average over the triplet states,assuming they are equally populated, shows up as a factor 1/3

Regards,
Olav

linqiaosong
Posts: 2
Joined: 08 Feb 2020, 06:14
First name(s): Qiaosong
Last name(s): Lin
Affiliation: Wuhan University
Country: China