一氧化钒阳离子VO(+)(X(3)Σ(-); v(+) = 0 - 3)的转动选择和分辨态到态光电子研究

Rotationally Selected and Resolved State-to-State Photoelectron Study of Vanadium Monoxide Cation VO(+)(X(3)Σ(-); v(+) = 0-3).

作者信息

Luo Zhihong, Chang Yih-Chung, Huang Huang, Ng C Y

机构信息

Department of Chemistry, University of California , Davis, California 95616, United States.

Department of Physics, Tsinghua University , Beijing 100084, China.

出版信息

J Phys Chem A. 2015 Nov 12;119(45):11162-9. doi: 10.1021/acs.jpca.5b09458. Epub 2015 Nov 3.

DOI:10.1021/acs.jpca.5b09458

PMID:26485180

Abstract

Vanadium monoxide cation VO(+)(X(3)Σ(-)) has been investigated by two-color visible (VIS)-ultraviolet (UV) pulsed field ionization-photoelectron (PFI-PE) methods. The unambiguous rotational assignment of rotationally selected and resolved VIS-UV-PFI-PE spectra thus obtained confirms the ground state term symmetry of VO(+) to be X(3)Σ(-). The rotational analysis also yields the rotational constants Be(+) = 0.5716 ± 0.0012 cm(-1) and αe(+) = 0.0027 ± 0.0005 cm(-1) for VO(+)(X(3)Σ(-)), from which the equilibrium bond distance of VO(+)(X(3)Σ(-)) is determined to be re(+) = 1.557 ± 0.002 Å. This PFI-PE study covers the vibrational bands, VO(+)(X(3)Σ(-); v(+) = 0, 1, 2, and 3) ← VO(X(4)Σ(-); v″ = 0), which has made possible the determination of the vibrational constants for VO(+)(X(3)Σ(-)) to be ωe(+) = 1068.0 ± 0.7 cm(-1) and ωe(+)xe(+) = 5.5 ± 0.7 cm(-1). The present state-to-state measurement also yields a more precise value (58 380.0 ± 0.7 cm(-1) or 7.238 20 ± 0.000 09 eV) for the ionization energy of VO [IE(VO)]. This value along with the known IE(V) has allowed the determination of the difference between the 0 K bond dissociation energy (D0) of VO(+)(X(3)Σ(-)) and that of VO(X(4)Σ(-)) to be D0(V(+)-O) - D0(V-O) = IE(V) - IE(VO) = -3967 ± 1 cm(-1).

摘要

一氧化钒阳离子VO(+)(X(3)Σ(-))已通过双色可见（VIS）-紫外（UV）脉冲场电离-光电子（PFI-PE）方法进行了研究。由此获得的经旋转选择和分辨的VIS-UV-PFI-PE光谱的明确旋转归属证实了VO(+)的基态项对称性为X(3)Σ(-)。旋转分析还得出VO(+)(X(3)Σ(-))的旋转常数Be(+) = 0.5716 ± 0.0012 cm(-1)和αe(+) = 0.0027 ± 0.0005 cm(-1)，据此确定VO(+)(X(3)Σ(-))的平衡键长为re(+) = 1.557 ± 0.002 Å。这项PFI-PE研究涵盖了振动带VO(+)(X(3)Σ(-); v(+) = 0, 1, 2, 和3) ← VO(X(4)Σ(-); v″ = 0)，这使得确定VO(+)(X(3)Σ(-))的振动常数成为可能，即ωe(+) = 1068.0 ± 0.7 cm(-1)和ωe(+)xe(+) = 5.5 ± 0.7 cm(-1)。当前的态-态测量还得出了VO的电离能[IE(VO)]的更精确值（58 380.0 ± 0.7 cm(-1)或7.238 20 ± 0.000 09 eV）。该值与已知的IE(V)一起使得确定VO(+)(X(3)Σ(-))和VO(X(4)Σ(-))在0 K时的键解离能（D0）之差成为可能，即D0(V(+)-O) - D0(V-O) = IE(V) - IE(VO) = -3967 ± 1 cm(-1)。