使用啁啾脉冲傅里叶变换微波（CP-FTMW）光谱对全氟丙酸一水合物和二水合物配合物的研究。

A Study of the Monohydrate and Dihydrate Complexes of Perfluoropropionic Acid Using Chirped-Pulse Fourier Transform Microwave (CP-FTMW) Spectroscopy.

作者信息

Grubbs G S, Obenchain Daniel A, Frank Derek S, Novick Stewart E, Cooke S A, Serrato Agapito, Lin Wei

机构信息

Department of Chemistry, Missouri University of Science and Technology , 400 W. 11th Street, Rolla, Missouri 65401, United States.

Department of Chemistry, Wesleyan University , 52 Lawn Avenue, Middletown, Connecticut 06459, United States.

出版信息

J Phys Chem A. 2015 Oct 22;119(42):10475-80. doi: 10.1021/acs.jpca.5b08347. Epub 2015 Oct 8.

DOI:10.1021/acs.jpca.5b08347

PMID:26421936

Abstract

This work reports the first known spectroscopic observation of the monohydrate and dihydrate complexes of perfluoropropionic acid (PFPA). The spectra have been observed using a chirped-pulse Fourier transform microwave (CP-FTMW) spectrometer in the 7750 to 14,250 MHz region. The structures of the species have been confirmed with the aid of ab initio quantum chemical calculations. Rotational constants A, B, and C have been determined and reported for both species along with centrifugal distortion constants ΔJ, ΔJK, ΔK, δJ, δK for H2O-PFPA and ΔJ, ΔJK, and δJ for (H2O)2-PFPA. Effects due to large amplitude motions were not observable in these experiments. Structures of the complexes have been determined using a combination of experimental second moment values and ab initio results. The complexation of the -OH of one or two water molecules has been found to occur in the plane of the carboxylic acid group forming a six- or eight-member ring.

摘要

这项工作报道了全氟丙酸（PFPA）一水合物和二水合物配合物首次已知的光谱观测结果。使用啁啾脉冲傅里叶变换微波（CP-FTMW）光谱仪在7750至14250 MHz区域观测到了这些光谱。借助从头算量子化学计算确定了这些物种的结构。已确定并报告了这两种物种的转动常数A、B和C，以及H₂O-PFPA的离心畸变常数ΔJ、ΔJK、ΔK、δJ、δK和(H₂O)₂-PFPA的ΔJ、ΔJK和δJ。在这些实验中未观察到大振幅运动的影响。已结合实验二阶矩值和从头算结果确定了配合物的结构。已发现一个或两个水分子的-OH在羧酸基团平面内发生络合，形成六元或八元环。