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外文期刊>journal of chemical physics
>On the perturbation of theBtilde;thinsp;2Arsquo;state of HCO by the 1thinsp;4Alsquo;and 1thinsp;4Arsquo;states: Surfaces of intersection and spinndash;orbit interactions
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On the perturbation of theBtilde;thinsp;2Arsquo;state of HCO by the 1thinsp;4Alsquo;and 1thinsp;4Arsquo;states: Surfaces of intersection and spinndash;orbit interactions
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机译：On the perturbation of theBtilde;thinsp;2Arsquo;state of HCO by the 1thinsp;4Alsquo;and 1thinsp;4Arsquo;states: Surfaces of intersection and spinndash;orbit interactions
The excitedBtilde;thinsp;2Arsquo;state of HCO is studied using multiconfiguration selfhyphen;consistent field/configuration interaction wave functions of 300thinsp;000 to 1thinsp;400thinsp;000 terms. Equilibrium structures for theXtilde;thinsp;2Arsquo;,Btilde;thinsp;2Arsquo;, 1thinsp;4Alsquo;, and 1thinsp;4Arsquo;states are determined as is theXtilde;thinsp;2Arsquo;ndash;Btilde;thinsp;2Arsquo;electronic transition dipole moment. This dipole transition moment vector is found to make an angle of sim;+34deg; with the inertialaaxis of theBtilde;thinsp;2Arsquo;state. The possibility of spinndash;orbit induced perturbation of the lowhyphen;lying vibrational levels of theBtilde;thinsp;2Arsquo;state attributable to the 1thinsp;4Alsquo;or 1thinsp;4Arsquo;states is considered. The minimum energy points on the surface of intersection of theBtilde;thinsp;2Arsquo;and 1thinsp;4Alsquo;states, denoted MECP(Btilde;thinsp;2Arsquo;ndash;1thinsp;4Alsquo;), and of theBtilde;thinsp;2Arsquo;and 1thinsp;4Arsquo;states, denoted MECP(Btilde;thinsp;2Arsquo;ndash;1thinsp;4Arsquo;), are determined. MECP(Btilde;thinsp;2Arsquo;ndash;1thinsp;4Alsquo;) is located very close to the 1thinsp;4Alsquo;equilibrium structure and is only sim;1500 cmminus;1above theBtilde;thinsp;2Arsquo;minimum. At MECP(Btilde;thinsp;2Arsquo;ndash;1thinsp;4Alsquo;) the parallel and perpendicular components of theBtilde;thinsp;2Arsquo;sim;1thinsp;4Alsquo;spinndash;orbit coupling, based on the microscopic Breitndash;Pauli operator, are approximately 50 and 4 cmminus;1, respectively. No barrier was found separating theBtilde;thinsp;2Arsquo;equilibrium structure and MECP(Btilde;thinsp;2Arsquo;ndash;4Alsquo;). MECP(Btilde;thinsp;2Arsquo;ndash;1thinsp;4Arsquo;) is close to the 1thinsp;4Arsquo;minimum and is placed sim;2400 cmminus;1above the minimum of theBtilde;thinsp;2Arsquo;state. However, theBtilde;thinsp;2Arsquo;sim;1thinsp;4Arsquo;spinndash;orbit interaction, a perpendicular interaction, is only sim;1 cmminus;1. Additional points on theBtilde;thinsp;2Arsquo;ndash;1thinsp;4Alsquo;surface of intersection and the correspondingBtilde;thinsp;2Arsquo;sim;1thinsp;4Alsquo;spinndash;orbit interactions are determined.
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