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标题: dalton磷光速率计算结果精确度问题 [打印本页]

作者
Author: shaowenhao28 时间: 2019-8-27 01:43
标题: dalton磷光速率计算结果精确度问题
各位老师好，我用dalton分别计算了同一个小分子（C,O,H,Br）的磷光速率和Tn-S0之间的SOCME，发现有些三重态虽然到基态的SOCME小，磷光速率却很大。

这是Tn-S0 SOCME的计算结果，删去了一些不相干的信息：
@ Excited state no: 1 in symmetry 1  ( A  )
----------------------------------------------

@ Excitation energy :  0.10245254    au
@                      2.7878753    eV; 22485.732    cm-1; 268.98909    kJ / mol

@ Total energy :    -3540.8493    au

@ Operator type: X1MNF-SO
@ Spin-orbit coupling constant (X1MNF-SO) : 4.3502780    cm-1
                                          1.98213254E-05 au

@ Operator type: Y1MNF-SO
@ Spin-orbit coupling constant (Y1MNF-SO) :  -3.2970288    cm-1
                                       -1.50223686E-05 au

@ Operator type: Z1MNF-SO
@ Spin-orbit coupling constant (Z1MNF-SO) :  -1.6351422    cm-1
                                       -7.45025631E-06 au

@ Excited state no: 2 in symmetry 1  ( A  )
----------------------------------------------

@ Excitation energy :  0.11357370    au
@                      3.0904977    eV; 24926.546    cm-1; 298.18771    kJ / mol

@ Total energy :    -3540.8382    au

@ Operator type: X1MNF-SO
@ Spin-orbit coupling constant (X1MNF-SO) : 22.893866    cm-1
                                          1.04312128E-04 au

@ Operator type: Y1MNF-SO
@ Spin-orbit coupling constant (Y1MNF-SO) :  -6.2197125    cm-1
                                       -2.83390955E-05 au

@ Operator type: Z1MNF-SO
@ Spin-orbit coupling constant (Z1MNF-SO) :  -4.8346676    cm-1
                                       -2.20283666E-05 au

@ Excited state no: 3 in symmetry 1  ( A  )
----------------------------------------------

@ Excitation energy :  0.12952635    au
@                      3.5245912    eV; 28427.747    cm-1; 340.07137    kJ / mol

@ Total energy :    -3540.8223    au

@ Operator type: X1MNF-SO
@ Spin-orbit coupling constant (X1MNF-SO) : 1.9424815    cm-1
                                          8.85059717E-06 au

@ Operator type: Y1MNF-SO
@ Spin-orbit coupling constant (Y1MNF-SO) : 1.1904373    cm-1
                                          5.42403134E-06 au

@ Operator type: Z1MNF-SO
@ Spin-orbit coupling constant (Z1MNF-SO) :  0.24867407    cm-1
                                          1.13304243E-06 au

可以看到就SOCME来说T2-S0 > T1-S0 > T3-S0，但是磷光速率的计算结果却显示kp的趋势是T3 > T2 > T1

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

Transition energy:  2.788 eV
or 444.726 nm

  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): X-polarization  17.210    Transition moment :  8.644E-04
  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): Y-polarization  5.5756    Transition moment :  4.920E-04
  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): Z-polarization  8.5183    Transition moment :  6.081E-04

  Phosphorescence - length gauge / mean field spin-orbit integrals:
Oscillator strength (/2PI)    (AMFI) 1.477296E-08
Dipole strength [a.u.]       (AMFI) 1.358989E-06
Dipole strength E-40 [esu**2 cm**2]    8.779712E-02
Total transition rate       (AMFI) 1.043476E+01 s-1
Total phosphorescence lifetime (AMFI) 9.583356E-02 s

Phosphorescence transition rate from excited state no.  2
(Triplet->singlet transition, high-temperature limit)

Transition energy:  3.090 eV
or 401.179 nm

  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): X-polarization  306.11    Transition moment :  3.123E-03
  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): Y-polarization  681.53    Transition moment :  4.660E-03
  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): Z-polarization  11.616    Transition moment :  6.084E-04

  Phosphorescence - length gauge / mean field spin-orbit integrals:
Oscillator strength (/2PI)    (AMFI) 3.837365E-07
Dipole strength [a.u.]       (AMFI) 3.184391E-05
Dipole strength E-40 [esu**2 cm**2]    2.057268E+00
Total transition rate       (AMFI) 3.330874E+02 s-1
Total phosphorescence lifetime (AMFI) 3.002215E-03 s

Phosphorescence transition rate from excited state no.  3
(Triplet->singlet transition, high-temperature limit)

Transition energy:  3.525 eV
or 351.769 nm

  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): X-polarization  478.39    Transition moment :  3.206E-03
  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): Y-polarization  3457.9    Transition moment :  8.619E-03
  Length gauge / mean field spin-orbit integrals:
Partial rates (AMFI): Z-polarization  93.818    Transition moment :  1.420E-03

  Phosphorescence - length gauge / mean field spin-orbit integrals:
Oscillator strength (/2PI)    (AMFI) 1.189904E-06
Dipole strength [a.u.]       (AMFI) 8.658146E-05
Dipole strength E-40 [esu**2 cm**2]    5.593573E+00
Total transition rate       (AMFI) 1.343376E+03 s-1
Total phosphorescence lifetime (AMFI) 7.443931E-04 s

请问计算结果可信吗？除了SOCME和能量差，是否还有别的因素会导致磷光速率反常？

另外附上输入文件
Tn-S0的SOCME:
**DALTON INPUT
.RUN RESPONS
**INTEGRALS
.MNF-SO
**WAVE FUNCTIONS
.DFT
B3LYP
**RESPONS
.TRPFLG
*LINEAR
.SINGLE RESIDUE
.PROPRT
X1MNF-SO
.PROPRT
Y1MNF-SO
.PROPRT
Z1MNF-SO
.PRINT
3
.ROOTS
5
**END OF DALTON INPUT

磷光速率：
**DALTON INPUT
.RUN RESPONS
**INTEGRALS
.MNF-SO
**WAVE FUNCTIONS
.DFT
B3LYP
**RESPONS
*QUADRATIC
.MNFPHO
.PRINT
3
.ROOTS
5
**END OF DALTON INPUT

作者
Author: abin 时间: 2019-8-27 09:13
basis set?

作者
Author: ggdh 时间: 2019-8-27 19:38
完全不顾kasha规则的么。。

作者
Author: shaowenhao28 时间: 2019-8-28 08:50

abin 发表于 2019-8-27 09:13
basis set?

basis set 是cc-pVDZ

作者
Author: shaowenhao28 时间: 2019-8-28 08:51

ggdh 发表于 2019-8-27 19:38
完全不顾kasha规则的么。。

kasha's rule应该只是在实验中体现吧，计算的时候算得是理论上如果从Tn发射时的磷光速率，不考虑internal convertion

作者
Author: abin 时间: 2019-8-28 12:41

shaowenhao28 发表于 2019-8-28 08:50
basis set 是cc-pVDZ

.MNF-SO
Calculates the atomic mean-field spin-orbit integrals as described in Ref. [138]. As the calculation of these integrals require a proper description of the atomic states, reliable results can only be expected for generally contracted basis sets such as the ANO sets, and in some cases also the correlation-consistent basis sets ((aug-)cc-p(C)VXZ)).

手册如此说的。不清楚， in some cases，是否包含你的情形。

作者
Author: 桀桀桀桀桀桀 时间: 2020-6-26 17:47
说来T2和T3的磷光发射速率不用乘上Boltzmann因子再和T1的比较吗？

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