In the pioneering work by R.A.Marcus,the solvation effect on electron transfer(ET)processes was investigated,giving rise to the celebrated nonadiabatic ET rate formula.In this work,on the basis of the thermodynamic so...In the pioneering work by R.A.Marcus,the solvation effect on electron transfer(ET)processes was investigated,giving rise to the celebrated nonadiabatic ET rate formula.In this work,on the basis of the thermodynamic solvation potentials analysis,we reexamine Marcus’formula with respect to the Rice-Ramsperger-Kassel-Marcus(RRKM)theory.Interestingly,the obtained RRKM analogue,which recovers the original Marcus’rate that is in a linear solvation scenario,is also applicable to the nonlinear solvation scenarios,where the multiple curve-crossing of solvation potentials exists.Parallelly,we revisit the corresponding Fermi’s golden rule results,with some critical comments against the RRKM analogue proposed in this work.For illustration,we consider the quadratic solvation scenarios,on the basis of physically well-supported descriptors.展开更多
Quantum mechanical and Rice-Ramsperger-Kassel-Marcus （RRKM） calculations are carried out to study the thermal unimolecular decomposition of 2,5-dihydrofuran （1）,2,5dihydrothiophene （2）,and 3-pyrroline （3） at t...Quantum mechanical and Rice-Ramsperger-Kassel-Marcus （RRKM） calculations are carried out to study the thermal unimolecular decomposition of 2,5-dihydrofuran （1）,2,5dihydrothiophene （2）,and 3-pyrroline （3） at the MPW1PW91/6-31＋＋G level of theory,and the results are in good agreement with the experimental values.The predicted high pressure limit rate constants （k（T）） in various states of activation energy and pre-exponential （S1：（A（calc.）,E a（calc.））,S2：（A （calc.）,E a（exp.））,and S3：（A （exp.）,E a（calc.））） for the thermal decomposition processes 1-3 were evaluated.Also,the fall-off pressures （P1/2） for compounds 1-3 in the states 1-3 are found to be （1.24×10-2,1.09×10-3,and 4.19×10-2mmHg）,（1.24×10-2,1.63×10-3,and 2.79×10-2mmHg）,and （1.24×10-2,1.63×10-3,and 4.19×10-2 mmHg）,respectively.As the fall-off pressure of thermal decomposition process of compounds 1-3 is in the following order：P1/2（3）〉 P1/2（1）〉 P1/2 （2）,the decomposition rates are as below：rate（3） 〈rate（1）〈rate（2）.展开更多
基金This work was supported by the Ministry of Science and Technology of China(No.2017YFA0204904 and No.2016YFA0400904)the National Natural Science Foundation of China(No.21633006),and Anhui Initiative in Quantum Information Technologies.
文摘In the pioneering work by R.A.Marcus,the solvation effect on electron transfer(ET)processes was investigated,giving rise to the celebrated nonadiabatic ET rate formula.In this work,on the basis of the thermodynamic solvation potentials analysis,we reexamine Marcus’formula with respect to the Rice-Ramsperger-Kassel-Marcus(RRKM)theory.Interestingly,the obtained RRKM analogue,which recovers the original Marcus’rate that is in a linear solvation scenario,is also applicable to the nonlinear solvation scenarios,where the multiple curve-crossing of solvation potentials exists.Parallelly,we revisit the corresponding Fermi’s golden rule results,with some critical comments against the RRKM analogue proposed in this work.For illustration,we consider the quadratic solvation scenarios,on the basis of physically well-supported descriptors.
文摘Quantum mechanical and Rice-Ramsperger-Kassel-Marcus （RRKM） calculations are carried out to study the thermal unimolecular decomposition of 2,5-dihydrofuran （1）,2,5dihydrothiophene （2）,and 3-pyrroline （3） at the MPW1PW91/6-31＋＋G level of theory,and the results are in good agreement with the experimental values.The predicted high pressure limit rate constants （k（T）） in various states of activation energy and pre-exponential （S1：（A（calc.）,E a（calc.））,S2：（A （calc.）,E a（exp.））,and S3：（A （exp.）,E a（calc.））） for the thermal decomposition processes 1-3 were evaluated.Also,the fall-off pressures （P1/2） for compounds 1-3 in the states 1-3 are found to be （1.24×10-2,1.09×10-3,and 4.19×10-2mmHg）,（1.24×10-2,1.63×10-3,and 2.79×10-2mmHg）,and （1.24×10-2,1.63×10-3,and 4.19×10-2 mmHg）,respectively.As the fall-off pressure of thermal decomposition process of compounds 1-3 is in the following order：P1/2（3）〉 P1/2（1）〉 P1/2 （2）,the decomposition rates are as below：rate（3） 〈rate（1）〈rate（2）.
基金supported by the Major Research Plan of the National Natural Science Foundation of China(91441132)Fundamental Research Funds for the Central Universities,China(3132016127,3132016326,3132016019)~~
基金supported by the Major Research Plan of the National Natural Science Foundation of China(91441132)Fundamental Research Funds for the Central Universities,China(3132016127,3132016326)~~
文摘使用MP2/6-311++G(2d,2p)方法和基组,计算了丁酸甲酯单分子解离反应体系详细的势能面。应用RRKM理论,计算了在1000-5000 K的温度范围内的正则系综的速率常数。与此同时,在微正则系综下,我们计算了温度为1000-5000 K对应的能量从451.92到1519.52 k J?mol^(-1)的速率常数。计算结果表明反应通道2、4和5的非谐振效应比较明显。因此对于丁酸甲酯单分子解离反应体系来说其非谐振效应是不能忽视的。
