<![CDATA[Pentadiynylidene and Its Methyl-Substituted Derivates: Threshold Photoelectron Spectroscopy of R1-C5-R2 Triplet Carbon Chains]]>

Engelbert Reusch; Dustin Kaiser; Domenik Schleier; Rachel Buschmann; Anke Krueger; Thomas Hermann; Bernd Engels; Ingo Fischer; Patrick Hemberger

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1-C₅-R₂ Triplet Carbon Chains]]>

机译：<！[CDATA [戊二炔基及其甲基取代衍生物：R _{1 -C _{5 -R _{2 三重碳链的阈值光电子谱 ]}}}

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Mass-selective threshold photoelectron spectroscopy in the gas phase was employed to characterize the dialkynyl triplet carbenes pentadiynylidene (HC_(5)H), methylpentadiynylidene (MeC_(5)H), and dimethylpentadiynylidene (MeC_(5)Me). Diazo compounds were employed as precursors to generate the carbenes by flash pyrolysis. The R_(1)-C_(5)-R_(2) carbon chains were photoionized by vacuum ultraviolet (VUV) synchrotron radiation in photoelectron photoion coincidence (PEPICO) experiments. High-level ab initio computations were carried out to support the interpretation of the experiments. For the unsubstituted pentadiynylidene (R_(1) = R_(2) = H) the recorded spectrum yields an adiabatic ionization energy (IE_(ad)) of 8.36 ± 0.03 eV. In addition, a second carbene isomer, 3-(didehydrovinylidene)cyclopropene, with a singlet electronic ground state, was identified in the spectrum based on the IE_(ad) of 8.60 ± 0.03 eV and Franck–Condon simulations. We found that multireference computations are required to reliably calculate the IE_(ad) for this molecule. CASPT2 computations predicted an IE_(ad) = 8.55 eV, while coupled-cluster computations significantly overestimate the IE. The cyclic isomer is most likely formed from another isomer of the precursor present in the sample. Stepwise methyl-substitution of the carbene leads to a reduction of the IE to 7.77 ± 0.04 eV for methylpentadiynylidene and 7.27 ± 0.06 eV for dimethylpentadiynylidene. The photoionization and dissociative photoionization of the precursors is investigated as well.

机译：气相中的质量选择性阈值光电子能量用于表征二炔基三重碳碳基（HC_（5）H），甲基戊二炔基（MEC_（5）H）和二甲基戊二炔基（MEC_（5）ME）。用闪热解采用DiaZo化合物作为前体以产生碳酸酯。通过真空紫外线（VUV）同步辐射在光电子光电巧合（Pepico）实验中通过真空紫外（VUV）同步辐射来照相r_（1）-C_（5）-R_（2）碳链。进行高级AB Initio计算以支持对实验的解释。对于未取代的五炔基（R_（1）= R_（2）= H），记录的光谱产生绝热电离能量（IE_（AD））为8.36±0.03eV。另外，基于8.60±0.03eV和Franck-Condon模拟的IE_（AD），在光谱中鉴定了第二个卡宾异构体，3-（丁酰酰基亚丙烯）环丙烯，以单向电子接地状态鉴定。我们发现，需要多次指定计算来可靠地计算该分子的IE_（AD）。 CASPT2计算预测IE_（AD）= 8.55eV，而耦合集群计算显着高估IE。环状异构体最有可能由样品中存在的前体的另一个异构体形成。逐步甲基取代甲苯导致甲基戊二炔基的IE至7.77±0.04eV和二甲基戊二炔基二炔基的7.27±0.06eV。还研究了前体的光离子和解离光照化。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2019年第10期|共10页
作者
Engelbert Reusch; Dustin Kaiser; Domenik Schleier; Rachel Buschmann; Anke Krueger; Thomas Hermann; Bernd Engels; Ingo Fischer; Patrick Hemberger;
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作者单位

Institute of Physical and Theoretical Chemistry University of Würzburg;

Institute of Physical and Theoretical Chemistry University of Würzburg;

Institute of Physical and Theoretical Chemistry University of Würzburg;

Institute of Organic Chemistry University of Würzburg;

Institute of Organic Chemistry University of Würzburg;

Institute of Physical and Theoretical Chemistry University of Würzburg;

Institute of Physical and Theoretical Chemistry University of Würzburg;

Institute of Physical and Theoretical Chemistry University of Würzburg;

Laboratory for Femtochemistry and Synchrotron Radiation Paul Scherrer Institut (PSI);

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正文语种 eng
中图分类物理化学（理论化学）、化学物理学;
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1. 1-C₅-R₂ Triplet Carbon Chains]]> [J] . Engelbert Reusch, Dustin Kaiser, Domenik Schleier, The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2019,第10期

机译：<！[CDATA [戊二炔基及其甲基取代衍生物：R _{1 -C _{5 -R _{2 三重碳链的阈值光电子谱 ]}}}
2. Neutral Cobalt-Carbonyl Bond Energy by Combined Threshold Photoelectron Photoion Coincidence and He(I) Photoelectron Spectroscopy [J] . Balint Sztaray, Laszlo Szepes, Tomas Baer The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2003,第44期

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机译：检测碳中的碳：利用差分充电通过X射线光电子能谱获得复合材料中碳纳米管聚集体的化学识别和空间位置信息
7. Pentadiynylidene and Its Methyl-Substituted Derivates: Threshold Photoelectron Spectroscopy of R1-C5-R2 Triplet Carbon Chains [O] . Engelbert Reusch, Dustin Kaiser, Domenik Schleier, 2019

机译：五炔基及其甲基取代衍生物：R1-C5-R2三重碳链的阈值光电子谱
8. High resolution threshold photoelectron spectroscopy by electron attachment [R] . Chutjian, A. 1979

机译：通过电子附着的高分辨率阈值光电子能谱

1-C5-R2 Triplet Carbon Chains]]>

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1-C₅-R₂ Triplet Carbon Chains]]>