Rotational spectra of twenty-one vibrational states of [35Cl]-and [37Cl]-chlorobenzene
Rotational spectra of twenty-one vibrational states of [35Cl]-and [37Cl]-chlorobenzene
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[35Cl]-和[37Cl]-氯苯的21个振动态的旋转光谱
DOI：
10.1016/j.jms.2023.111776
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发表时间：
2023
影响因子：
1.4
通讯作者：
McMahon, Robert J.
中科院分区：
文献类型：
--
作者：
Dorman, P. Matisha;Esselman, Brian J.;Changala, P. Bryan;McCarthy, Michael C.;Woods, R. Claude;McMahon, Robert J.
本文研究了[~（35）Cl]-和[~（37）Cl]-氯苯（C_6H_5Cl）在2 ~ 18 GHz和130-360 GHz的转动光谱，测量、归属和最小二乘拟合了21个振动态的近40，000个跃迁。先前测量的[35 Cl]-和[37 Cl]-氯苯基态跃迁与新测量的跃迁相结合，并拟合到A-约化的部分六次哈密顿模型，误差低（σ总拟合<0.05 MHz）。分析2-18 GHz的频谱允许细化的核超精细耦合常数的基态光谱的两种同位素，而测量的130-360 GHz的频谱提供了足够的信息，以确定第一次的基态的六次离心畸变常数。根据室温下收集的毫米波数据，测定了[~（35）Cl]-氯苯（ν20，ν30，ν11，ν14，ν19，ν 29和ν18）和[~（37）Cl]-氯苯（ν20，ν30，ν11）的最低能量基本光谱常数。与以前的研究氯代芳烃，计算的（B3 LYP/6-311+G（2d，p））光谱常数显示出相当接近的协议与实验测定值。
The rotational spectra of [35Cl]- and [37Cl]-chlorobenzene (C6H5Cl) have been studied from 2 to 18 GHz and 130–360 GHz, resulting in the measurement, assignment, and least-squares fitting of almost 40,000 transitions of twenty-one vibrational states. Previously measured [35Cl]- and [37Cl]-chlorobenzene ground-state transitions were combined with newly measured transitions and fit to A-reduced, partial sextic Hamiltonian models with low-error (σtotal fit<0.05 MHz). Analysis of the 2–18 GHz spectrum allowed for refinement of the nuclear hyperfine coupling constants for the ground-state spectra of both isotopologues, while measurement of the 130–360 GHz spectrum provided sufficient information to determine the sextic centrifugal distortion constants of the ground states for the first time. From these millimeter-wave data collected at room temperature, the spectroscopic constants for the lowest-energy fundamentals of [35Cl]-chlorobenzene (ν20, ν30, ν11, ν14, ν19, ν29and ν18) and [37Cl]-chlorobenzene (ν20, ν30, ν11) were determined. As with previous studies of chloroarenes, the computed (B3LYP/6–311+G(2d,p)) spectroscopic constants show quite close agreement with the experimentally determined values.