劉曉軍，劉鑫鵬，徐林軒，王歡，任曉輝，李瑞，楊研

PF+分子離子激發(fā)態(tài)的理論研究

劉曉軍1，劉鑫鵬1，徐林軒1，王歡1，任曉輝1，李瑞1，楊研2

（齊齊哈爾大學 1. 理學院，2. 教育督導室，黑龍江 齊齊哈爾 161006）

PF+；勢能曲線；光譜常數(shù)；弗蘭克-康登因子

1 計算方法

2 結(jié)果與討論

2.1 PF+分子離子的態(tài)的勢能曲線和光譜常數(shù)

參考Winger-Witmer規(guī)則，通過解離極限原子的電子狀態(tài)確定分子的電子狀態(tài)，即

圖1 PF+分子離子的第一解離極限態(tài)的勢能曲線

表1　PF+分子離子的Λ-S態(tài)的光譜常數(shù)

注：a Ref[6]；b Ref[17]．

表2 PF+分子離子的束縛態(tài)（）的振動能級

續(xù)表

2.2 PF+分子離子的態(tài)電偶極距

圖2 態(tài)的電偶極矩隨核間距的變化

2.3 PF+分子離子的弗蘭克-康登因子和愛因斯坦系數(shù)

表3 分子離子激發(fā)態(tài)躍遷的Franck-Condon因子

表4 分子離子的愛因斯坦系數(shù)

３ 結(jié)論

[1] Zhao Y，Setser D W．Radiative Lifetime and Quenching Rate Constants of PF（b1 SIGMA+）and Tests for an Electronic to Vibrational Energy Transfer Quenching Mechanism[J]．J Phys Chem，1994，98：9723-9734

[2] Zhao Y，Setser D W．Quenching rate constants for NCl（b1Σ+）and PCl（b1Σ+）and radiative lifetimes of NCl（b1Σ+），PCl（b1Σ+）and PBr（b1Σ+）[J]．J Chem Soc，F(xiàn)araday Trans，1995，91：2979-2987

[3] Butcher V，Dyke J M，Lewis A E，et al．A study of the ground electronic states of the isoelectronic ions PF+and NCI+by vacuum ultraviolet photoelectron spectroscopy[J]．J Chem Soc，F(xiàn)araday Trans，1988，284：299-310

[4] Yu L，Bian W．Electronically excited-state properties and predissociation mechanisms of phosphorus monofluoride：A theoretical study including spin orbit coupling[J]．The Journal of Chemical Physics，2012，137：014313-1-12

[5] Liu H，Shi D，Sun J，et al．Multireference configuration interaction study of the 27 low-lying states of the PF+cation Spectrochimica[J]．Acta Part A：Molecular and Biomolecular Spectroscopy，2017，38：181-226

[6] Douglas A E，F(xiàn)rackowiak M．The Electronic Spectra of Pf and PF+[J]．Can J Phys，1962，40：832-849

[7] Berkowitz J，Greene J P，Jr J F，et al．Bonding and ionization energies of NF and PF compounds[J]．The Journal of Chemical Physics，1984，81：6166-6175

[8] Kim G-S，Hirst D M．Excited states of the PF+$ and NCl+$ ions：a theoretical treatment[J]．Molecular Physics，1995，85：463－475

[9] Li Q-N，Zhao S-T，Zhang X-M，et al．A Precise Description of the Electronic Structures and Spin-Allowed Transition Properties of PF and Its Cation：All-Electron Configuration-Interaction Investigations Including Relativistic Effect[J]．Chinese Phys Lett, 2015，32：73-103

[10] Werner H J，Knowles P J，Knizia G，et al. Molpro: a general purpose quantum chemistry program package[J]．WIREs Comput Mol Sci，2012，2：242-253

[11] Werner H J，Knowles P J．A Second Order Multiconfiguration SCF Procedure with Optimum Convergence[J]. J Chem Phys，1985， 82：5053-5063

[12] Knowles P J，Werner H J．An Efficient Second-Order MCSCF Method for Long Configuration Expansions[J]．Chem Phys Lett， 1985，115：259-267

[13] Werner H J，Knowles P J．An Efficient Internally Contracted Multiconfiguration-Reference Configuration Interaction Method[J]．J Chem Phys，1988，89：5803-5814

[14] Knowles P J，Werner H J. An Efficient Method for the Evaluation of Coupling Coefficients in Configuration Interaction Calculations[J]．Chem Phys Lett，1988，145：514-522

[15] Langhoff S R，Davidson E R．Configuration Interaction Calculations on the Nitrogen Molecule[J]．Int J Quantum Chem，1974， 8：61-72

[16] Le Roy，LEVEL R J．A computer program for solving the radial Schr?dinger equation for bound and quasibound levels[D]．Chemical Physics Research Report CP-661，Ontario，Canada：University of Waterloo，2005

[17] Nguyen M T．Ab initio calculations on low-lying electronic states of the PX，PX+and PX-species（X = H，F(xiàn) and Cl）[J]．Molecular Physics，1986，59，547-558

The oretical investigations on excited states of PF+

LIU Xiaojun1，LIU Xinpeng1，XU Linxuan1，WANG Huan1，REN Xiaohui1，LI Rui1，YANG Yan2

（1. School of Science，2. Office of Educational Supervision Organization，Qiqihar University，Qiqihar 161006，China）

PF+；potential energy curves；spectroscopic constants；Franck-Condon factor

O-561

A

10.3969/j.issn.1007-9831.2020.11.009

1007-9831（2020）11-0036-06

2020-08-22

黑龍江省教育廳項目（135209258）；齊齊哈爾大學教育科學研究項目（2017026）；齊齊哈爾大學學位與研究生教育教學改革研究項目（JGXM_QUG_2019011）

劉曉軍（1972-），男，黑龍江齊齊哈爾人，副教授，碩士，從事分子光譜、光學研究．E-mail：liuxiaojun@qqhru.edu.cn