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无辐射跃迁理论进展
- 牛英利1, 林至闓2, 杨玲3, 于建国4, 何荣幸5, 庞然6, 朱超原*2, 林倫年7, 林聖賢2
作者信息
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Recent Developments in Radiationless Transitions
- Niu Yingli1, Lin Chinkai2, Yang Ling3, Yu Jianguo4, He Rongxing5, Pang Ran6, Zhu Chaoyuan2, Hayashi Michitoshi7, Lin Sheng Hsien2
Author information
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文章历史
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摘要
在本文中,我们将介绍运用第一性原理计算包含非谐效应或势能面锥形交叉情况下内转换速率的最新工作。我们同时计算了包含非谐效应的分子吸收和发射光谱,以检验量子化学方法计算得到势能面的准确性。势能面的锥形交叉对内转换过程的影响是学界广泛关注的焦点。本文将介绍如何在内转换速率计算的过程中考虑势能面锥形交叉的影响,并将之运用于吡嗪分子。本文运用绝热近似理论处理了另外一个重要的无辐射过程,分子的振动驰豫过程,并将这个理论应用于水二聚体和苯胺的振动弛豫速率的计算。
Abstract
In this paper, we will introduce recent works on the mathematical treatments and the first-principle calculations concerning the internal conversion rates for the cases with anharmonic potentials, and conical intersecting potentials. The simulations of absorption and emission spectra with anharmonic effects are also presented to check the validity of the potential energy surfaces obtained from the quantum chemical calculations. The effect of conical intersection on internal conversion has attracted considerable attention. In this paper a different approach will be proposed and applied to pyrazine. Another important non-radiative process, molecular vibrational relaxation, is also treated by applying the adiabatic approximation to the ab initio anharmonic potential energy surfaces in this paper. The vibrational relaxation rates in water dimer and aniline are chosen to demonstrate the calculation.
关键词
无辐射跃迁 / 内转换 / 振动弛豫 / 双井势 / 非谐效应 {{custom_keyword}} /
Key words
radiationless transition / internal conversion / vibrational relaxation / double well potential / anharmonic effect {{custom_keyword}} /
中图分类号：
O643.3
TQ51
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参考文献
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[2] Englman R, Jortner J. Mol. Phys., 1970, 182): 145-164
[3] Freed F, Jortner J. J. Chem. Phys., 1970, 5212): 6272-6291
[4] Nitzan A, Jortner J. J. Chem. Phys., 1971, 553): 1355-1368
[5] Siebrand W. J. Chem. Phys., 1971, 541): 363-367
[6] Fischer S. Chem. Phys. Lett., 1971, 115): 577-582
[7] Lin S H, Bersohn R. J. Chem. Phys., 1968, 486): 2732-2736
[8] Henry B R, asha M. Annu. Rev. Phys. Chem., 1968, 191): 161-192
[9] Huang , Rhys A. Proc. R. Soc. Lond. A., 1950, 204: 406-423
[10] Huang . Contemp. Phys., 1981, 226): 599-612
[11] Duschinsky F. Acta Physicochim. USSR)., 1937, 7: 551
[12] Hayashi M, Mebel A M, Liang , Lin S H. J. Chem. Phys., 1998, 1085): 2044-2055
[13] Mebel A M, Hayashi M, Liang , Lin S H. J. Phys. Chem. A., 1999, 10350): 10674-10690
[14] Peng Q, Yi Y, Shuai , Shao J. J. Chem. Phys., 2007, 126: art. no. 114302
[15] Peng Q, Yi Y, Shuai , Shao J. J. Am. Chem. Soc., 2007, 129: 9333-9339
[16] Niu Y, Peng Q, Shuai . Sci. China Ser. B-Chem., 2008, 5112): 1153-1158
[17] Tang J, Lee M T, Lin S H. J. Chem. Phys., 2003, 11914): 7188-7196
[18] Islampour R, Miralinaghi M. J. Phys. Chem. A., 2007, 11138): 9454-9462
[19] Islampour R, Miralinaghi M. J. Phys. Chem. A., 2009, 11311): 2340-2349
[20] Pople J A, Sidman J W. J. Chem. Phys., 1957, 276): 1270-1277
[21] Robinson G W, Digiorgio V E. Can. J. Chem., 1958, 361): 31-38
[22] Callomon J H, Innes . J. Mol. Spectrosc., 1963, 101/6): 166-181
[23] Job V A, Sethuraman V, Innes . J. Mol. Spectrosc., 1969, 301/3): 365-426
[24] Moule D C, Walsh A D. Chem. Rev., 1975, 751): 67-84
[25] Miller R G, Lee E C. J. Chem. Phys., 1978, 6810): 4448-4464
[26] Strickler S J, Barnhart R J. J. Phys. Chem., 1982, 864): 448-455
[27] Jensen P, Bunker P R. J. Mol. Spectrosc., 1982, 941): 114-125
[28] Clouthier D J, Ramsay D A. Ann. Rev. Phys. Chem., 1983, 341): 31-58
[29] Reisner D E, Field R W, insey J L, Dai H. J. Chem. Phys., 1984, 8012): 5968-5978
[30] Lin C , Chang H C, Lin S H. J. Phys. Chem. A., 2007, 11138): 9347-9354
[31] Coon J B, Naugle N W, Mckenzie R D. J. Mol. Spectrosc., 1966, 202): 107-129
[32] Lin S H, Eyring H. Proc. Nat. Acad. Sci. USA., 1974, 719): 3415-3417
[33] Lin S H. Proc. R. Soc. Lond. A., 1976, 352 1668): 57-71
[34] Lin S H, Fujimura Y, Neusser H J, Schlag E W. Multiphoton Spectroscopy of Molecules. New York: Academic Press, 1984
[35] Yeung E S, Moore C B. J. Chem. Phys., 1973, 589): 3988-3998
[36] Miller R G, Lee E C. Chem. Phys. Lett., 1975, 331): 104-107
[37] Miller R G, Lee E C. Chem. Phys. Lett., 1976, 411): 52-54
[38] Yeung E S, Moore C B. J. Chem. Phys., 1974, 605): 2139-2147
[39] Tang Y, Fairchild P W, Lee E C. J. Chem. Phys., 1977, 667): 3303-3305
[40] Liang , Chang R, Hayashi M, Lin S H. Principle of Molecular Spectroscopy and Photochemistry. Taichung: National Chung Hsing University Press, 2001
[41] Lin C, Li M, Yamaki M, Hayashi M, Lin S H. Phys. Chem. Chem. Phys., 2010, 1237): 11432-11444
[42] hu C, Liang , Hayashi M, Lin S H. Chem. Phys., 2009, 3581／2): 137-146
[43] Wang H, hu C, Yu J, Lin S H. J. Phys. Chem. A., 2009, 11352): 14407-14414
[44] Villa E, Amirav A, Lim E C. J. Phys. Chem., 1988, 9219): 5393-5397
[45] Mochizuki Y, aya , Ito M. J. Chem. Phys., 1978, 692): 935-936
[46] Yang L, hu C Y, Yu J G, Lin S H. Chem. Phys., to be published).
[47] Da Silva F F, Almeida D, Martins G, Milosavljevic A R, Marinkovic B P, Hoffmann S V, Mason N J, Nunes Y, Garcia G, Limao-Vieira P. Phys. Chem. Chem. Phys., 2010, 1225)
[48] night A E W, Lawburgh C M, Parmenter C S. J. Chem. Phys., 1975, 6310): 4336-4351
[49] Butler P, Moss D B, Yin H, Schmidt T W, able S H. J. Chem. Phys., 2007, 1279): 94303
[50] Lin S H. J. Chem. Phys., 1973, 5812): 5760-5768
[51] Werner H J, nowles P J, Lindh R, Manby F R, Celani P, orona T, Rauhut G, Amos R D, Bernhardsson A, Berning A, Cooper D L, Dobbyn A J, Eckert F, Hampel C, Hetzer G, Lloyd A W, Mcnicholas S J, Meyer W, Mura M E, Nicklaβ A, Palmieri P, Pitzer R, Schumann U, Stoll H, Tarroni R, Thorsteinsson T. Molpro. 2006
[52] Abramson A S, Spears G, Rice S A. J. Chem. Phys., 1972, 565): 2291-2308
[53] He R X, Yang L, hu C Y, Yamaki M, Lee Y P, Lin S H. J. Chem. Phys., 2011, 1349): 94313
[54] Seidner L, Stock G, Sobolewski A L, Domcke W. J. Chem. Phys., 1992, 967): 5298-5309
[55] Woywod C, Domcke W, Sobolewski A L, Werner H. J. Chem. Phys., 1994, 1002): 1400-1413
[56] Seel M, Domcke W. J. Chem. Phys., 1991, 9511): 7806-7822
[57] Suzuki Y, Fuji T, Horio T, Suzuki T. J. Chem. Phys., 2010, 13217): 174302
[58] Werner U, Mitric R, Suzuki T, Bonacic-outeck V. Chem. Phys., 2008, 3491-3): 319-324
[59] Innes , Ross I G, Moomaw W R. J. Mol. Spectrosc., 1988, 1322): 492-544
[60] Lin C , Niu Y L, hu C Y, Shuai G, Lin S H. Chem. Asian J., 2011, 611): 2977-2985
[61] Laubereau A, aiser W. Rev. Mod. Phys., 1978, 503): 607-665
[62] Nesbitt D J, Field R W. J. Phys. Chem., 1996, 10031): 12735-12756
[63] Voth G A, Hochstrasser R M. J. Phys. Chem., 1996, 10031): 13034-13049
[64] Barone V. J. Chem. Phys., 2005, 1221): 14108
[65] Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Scalmani G, Barone V, Mennucci B, Petersson G A, Nakatsuji H, Caricato M, Li X, Hratchian H P, Izmaylov A F, Bloino J, heng G, Sonnenberg J L, Hada M, Ehara M, Toyota , Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, itao O, Nakai H, Vreven T, Montgomery J J A, Peralta J E, Ogliaro F, Bearpark M, Heyd J J, Brothers E, udin N, Staroverov V N, obayashi R, Normand J, Raghavachari , Rendell A, Burant J C, Iyengar S S, Tomasi J, Cossi M, Rega N, Millam N J, lene M, nox J E, Cross J B, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann R E, Yazyev O, Austin A J, Cammi R, Pomelli C, Ochterski J W, Martin R L, Morokuma , akrzewski V G, Voth G A, Salvador P, Dannenberg J J, Dapprich S, Daniels A D, Farkas Ö, Foresman J B, Ortiz J V, Cioslowski J, Fox D J. Gaussian 09. Gaussian, Inc.
[66] Yanai T, Tew D P, Handy N C. Chem. Phys. Lett., 2004, 3931／3): 51-57
[67] Huang S, Miller R E. J. Chem. Phys., 1989, 9111): 6613-6631
[68] Yamada Y, Okano J, Mikami N, Ebata T. Chem. Phys. Lett., 2006, 4324-6): 421-425
[69] Yamada Y, Okano J, Mikami N, Ebata T. J. Chem. Phys., 2005, 12312): 124316
[70] Ebata T, Minejima C, Mikami N. J. Phys. Chem. A., 2002, 10646): 11070-11074
[71] Hutchinson J S, Reinhardt W P, Hynes J T. J. Chem. Phys., 1983, 799): 4247-4260
[72] Ebata T, ayano M, Sato S, Mikami N. J. Phys. Chem. A., 2001, 10538): 8623-8628
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