The 235–360 GHz Rotational Spectrum of 1-Oxaspiro[2.5]octa-4,7-dien-6-one─Analysis of the Ground Vibrational State and Its 10 Lowest-Energy Vibrationally Excited States
The 235–360 GHz Rotational Spectrum of 1-Oxaspiro[2.5]octa-4,7-dien-6-one─Analysis of the Ground Vibrational State and Its 10 Lowest-Energy Vibrationally Excited States
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1-Oxspiro[2.5]octa-4,7-dien-6-one 的 235～360 GHz 旋转频谱——地面振动状态及其 10 个最低能量振动激发状态的分析
DOI：
10.1021/acs.jpca.3c07049
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发表时间：
2024
期刊：
影响因子：
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通讯作者：
McMahon, Robert J.
中科院分区：
文献类型：
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作者：
Esselman, Brian J.;Pimentel, Edward B.;Styers, William H.;Jean, Dairen R.;Woods, R. Claude;McMahon, Robert J.
在235 ~ 360 GHz范围内，测量了1-氧杂螺[2.5]辛-4，7-二烯-6-酮（1）的毫米波转动谱。首次获得了该化合物的转动光谱，观测到5500多个a-和c-型跃迁，并将其归属于振动基态。这些转变是最小二乘拟合S-和A-减少，六次扭曲转子哈密顿在Irrepresentation（σ拟合= 37 kHz）。此外，四种基本状态的转变（ν22，ν21，ν39和ν38），四个泛音状态（2ν22、3ν22、4ν22和5ν22）和两个组合态（ν22+ ν 21和ν22+ ν39）被测量、分配，并最小二乘拟合到Irrepresentation中的单态、S-和A-约化的六次扭曲转子哈密顿量（σfit< 42 kHz）。计算的振动-转动相互作用常数（B 0-Bv）（MP2和B3 LYP/6-311+G（2d，p））与相应的实验值进行了比较，显示出所有基态的良好一致性。根据v ν 22系列6个成员的跃迁强度，确定v ν 22的基频为79.0（2.1）cm-1。
The millimeter-wave rotational spectrum of 1-oxaspiro[2.5]octa-4,7-dien-6-one (1) was collected from 235 to 360 GHz. With the rotational spectrum of this compound available for the first time, more than 5500a- andc-type transitions were observed and assigned for the vibrational ground state. These transitions were least-squares fit to S- and A-reduced, sextic distorted-rotor Hamiltonians in the Irrepresentation (σfit= 37 kHz). Additionally, transitions of four fundamental states (ν22, ν21, ν39, and ν38), four overtone states (2ν22, 3ν22, 4ν22, and 5ν22), and two combination states (ν22+ ν21and ν22+ ν39) were measured, assigned, and least-squares fit to single-state, S- and A-reduced, sextic distorted-rotor Hamiltonians in the Irrepresentation (σfit< 42 kHz). The computed vibration–rotation interaction constants (B0–Bv) (MP2 and B3LYP/6-311+G(2d,p)) were compared to their corresponding experimental values, showing excellent agreement for all fundamental states. Based on the intensities of the transitions from six members of the v ν22series, the fundamental frequency of ν22was determined to be 79.0 (2.1) cm–1.