Spectroscopic Properties About Loy-lying Electronic States Of BS~+ Cation And PN~+ Cation

The molecular potential energy function is one of the theoretical basis of mechanical properties,electronic structure,geometric properties and spectrum properties that we have researched.To discuss the potential energy function,we will begin from the most basic physics system-diatomic molecules system,so the diatomic molecular potential energy function of the analytic form and its potential curve are the mainly exploration parts of the atom molecule physics subject.Elements of N,P,S as well as their compounds and their free radicals arouse strong interest in physics and chemistry experiments.For BS⁺ ions,its spectroscopy characteristics plays a very important role in the study of astrophysics.But throughout the past 10 years,only a few spectroscopy experimental data and theory data are reported.So our job is to extend the spectroscopy of BS⁺ ion.And for PN⁺ ions,it has a very important role in the process of atmospheric composition and burning,only a small number of measured spectroscopy data and calculated spectroscopy data is reported in the literature,especially its spectroscopy data of ? state is not recorded in the previous literature,so we will through the study of the potential energy curve in order to expand its spectroscopy data in this article.In this article,we study the spectroscopic properties of BS⁺ ion and PN⁺ ion,the spectroscopic properties include potential energy curves,spectroscopic parameters,transition properties and so on.In addition,in order to improve the accuracy of the computation,the effects on the spectroscopic parameters by some corrections are introduced into the calculation.In the process of calculation,we first use the complete active space self-consistent field?CASSCF?method to obtain optimum orbital,then use the multireference configuration interaction method?ic MRCI⁺Q?to calculate,in this process we havecombined large consistent basis,next through MOLPRO2010.1 package the molecular potential energy curve?PECs?is obtained.In the above calculation,the scalar relativistic correction?DK correction?,nuclear price related correction?CV?as well as to the total energy of the group of extrapolation are considered.The fitting was conducted in the MOLCAS program,and through solving radial Schrodinger equation to obtain corresponding ion spectrum constant of various electronic state and molecular constants.In addition,the spin-orbit coupling effect of ? state is through the configuration interaction method of combining Breit-Pauli Hamiltonian operator for operation.Firstly,the potential energy curves of 10 ?–S states of BS⁺ yielded from the first four dissociation limits are calculated with the theoretical calculation methods,its internuclear separations is from about 0.12 to 0.70 nm.According to the further research of 10 ?–S states,we found that 2¹?⁺ is a double potential state,its first potential well will disappear as the increasing of AVn Z.2³?-is a double potential state,and it has avoided crossing.Another double potential state is 2³?,and its second potential well is very weakly-bound one.In addition,the transition dipole moments,the Franck-Condon factors and the radiative times of the transitions 2³?0--1³?2,2³?0⁺-1³?2,2³?-0-1³?2 and 2³?-0-1³?2 are calculated.We have also calculated the potential energy curves,the spectroscopic parameters and the Dominant ?-S states at Re of 25? states.Secondly,we calculate the potential energy curves?PECs?of 9 ?-S states?X²?⁺,1⁴?⁺,1⁶?⁺,A²?,1⁴?,1⁶?,1⁴?,1⁴?-,2⁴??and corresponding 28 ? states of PN⁺ cation.In the 9 ?-S states,2⁴?,1⁶? and 1⁴?-are double potential states,the second well of them are very weakly-bound ones,the study also found that the1⁶? and 2⁶?,2⁴? and 3⁴? have the avoided crossings.The transition dipole moments,the Franck-Condon factors and the radiative times of transitions 1⁶?_-1/2?the first potential well?-X²?⁺_1/2 and 2⁴?_-1/2?the first potential well?-X²?⁺_1/2 are discussed.In calculations,using the complete active space self-consistent field?CASSCF?,which is followed by the internally contracted multireference configuration interaction?ic MRCI?with Davidson modification,and through the MOLPRO 2010.1 packages,we obtain the potential energy curves?PECs?and the spectroscopic parameters.In the above calculations,core-valence correlation,scalar relativistic correction and the total energy extrapolated to the complete basis set limit are included,The spin-orbit coupling effect is accounted for by the state interaction method with the Breit-Pauli Hamiltonian.Finally,the spectroscopic parameters are evaluated,and compared with available measurements and other theoretical results,we find that an expansion of theoretical data of BS⁺ ions and PN⁺ ions have filled the ions on the spectrum constant vacancy.And some states are reported for the first time,although we can't compare with previous theoretical value,through its comparison with the experimental data,we find that the data is consistent with each other.This effectively shows that the theory method that we selected and the data that we obtained are very reliable.