H3PAgI: generation by laser-ablation and characterization by rotational spectroscopy and ab initio calculations.
H3PAgI: generation by laser-ablation and characterization by rotational spectroscopy and ab initio calculations.
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DOI：
10.1039/c6cp03512d
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发表时间：
2016-07-28
期刊：
影响因子：
--
通讯作者：
Legon AC
中科院分区：
文献类型：
--
作者：
Stephens SL;Tew DP;Walker NR;Legon AC
用激光烧蚀金属银，在氩气中用ICF_3和PH_3的混合气体脉冲反应，在气相中合成了新化合物H_3 P···AgI。用激光烧蚀金属银，在氩气中用ICF_3和PH_3的混合气体脉冲反应，在气相中合成了新化合物H_3 P···AgI。利用啁啾脉冲傅里叶变换微波光谱仪检测并归属了自然丰度的两种同位素H3 P····107 AgI和H3 P···109 AgI的基态转动光谱。这两种同位素都显示出螺旋陀螺型的转动光谱，通过分析得到了转动常数B 0、四次离心畸变常数DJ和DJK以及碘核四极耦合常数χ aa（I）= eQq aa的精确值。在CCSD（T）（F12*）/aug-cc-pVDZ显关联水平上的从头算计算结果表明，P···Ag-I原子按此顺序位于C3轴上.根据实验结果，计算得到的键长r 0（P···Ag）= 2.3488（20）和r 0（Ag-I）= 2.5483（1），与从头计算得到的平衡键长r 0（P···Ag）= 2.3387和r 0（Ag-I）= 2.5537一致.本文给出了PH 3与AgI相互作用强度的量度（H3 P···AgI = H3 P + AgI的离解能De和分子间拉伸力常数FP···Ag），并解释了它们与金属键合的分子及其卤素键合和氢键合的类似物的结合强度的顺序为H3 P···HI <H3 P···ICl <H3 P···AgI。
The new compound H3P···AgI has been synthesized in the gas phase by means of the reaction of laser-ablated silver metal with a pulse of gas consisting of a dilute mixture of ICF3 and PH3 in argon. The new compound H3P···AgI has been synthesized in the gas phase by means of the reaction of laser-ablated silver metal with a pulse of gas consisting of a dilute mixture of ICF3 and PH3 in argon. Ground-state rotational spectra were detected and assigned for the two isotopologues H3P···107AgI and H3P···109AgI in their natural abundance by means of a chirped-pulse, Fourier-transform, microwave spectrometer. Both isotopologues exhibit rotational spectra of the symmetric-top type, analysis of which led to accurate values of the rotational constant B 0, the quartic centrifugal distortion constants D J and D JK , and the iodine nuclear quadrupole coupling constant χ aa (I) = eQq aa . Ab initio calculations at the explicitly-correlated level of theory CCSD(T)(F12*)/aug-cc-pVDZ confirmed that the atoms P···Ag–I lie on the C 3 axis in that order. The experimental rotational constants were interpreted to give the bond lengths r 0(P···Ag) = 2.3488(20) Å and r 0(Ag–I) = 2.5483(1) Å, in good agreement with the equilibrium lengths of 2.3387 Å and 2.5537 Å, respectively, obtained in the ab initio calculations. Measures of the strength of the interaction of PH3 and AgI (the dissociation energy D e for the process H3P···AgI = H3P + AgI and the intermolecular stretching force constant F P···Ag) are presented and are interpreted to show that the order of binding strength is H3P···HI < H3P···ICl < H3P···AgI for these metal-bonded molecules and their halogen-bonded and hydrogen-bonded analogues.
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影响因子：
4.4
作者：
DOLG, M;WEDIG, U;PREUSS, H
通讯作者：
PREUSS, H
影响因子：
4.4
作者：
Bittner, Dror M.;Zaleski, Daniel P.;Legon, Anthony C.
通讯作者：
Legon, Anthony C.
影响因子：
4.4
作者：
DAILEY, BP;TOWNES, CH
通讯作者：
TOWNES, CH
影响因子：
16.6
作者：
Francis, Simon G.;Matthews, Steven L.;Legon, Anthony C.
通讯作者：
Legon, Anthony C.
DOI：
10.1039/ft9918700507
发表时间：
1991-02-21
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS
影响因子：
--
作者：
HOWARD, NW;LEGON, AC;LUSCOMBE, GJ
通讯作者：
LUSCOMBE, GJ