Mass analyzed threshold ionization detected infrared spectroscopy: isomerization activity of the phenol-Ar cluster near the ionization threshold.
Mass analyzed threshold ionization detected infrared spectroscopy: isomerization activity of the phenol-Ar cluster near the ionization threshold.
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质量分析阈值电离检测红外光谱：苯酚-Ar簇在电离阈值附近的异构化活性
DOI：
10.1039/c4cp04584j
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
M. Fujii
中科院分区：
文献类型：
--
作者：
M. Miyazaki;S. Yoshikawa;F. Michels;K. Misawa;S. Ishiuchi;M. Sakai;O. Dopfer;K. Müller-Dethlefs;M. Fujii
用质量分析阈电离探测红外光谱（MATI-IR）技术研究了酚氩团簇（PhOH-Ar）的高n里德堡态结构.该方法选择性地测量分子团簇在非常高n Rydberg态（n > 100）下的红外光谱，所述分子团簇在零动能（ZEKE）光电子和MATI光谱中使用，其离子核心基本上与相应的裸阳离子相同。当中性基态（S 0）的π束缚簇通过S1原点共振激发到里德堡态并收敛到其绝热电离能级IE 0（π）时，MATI-IR光谱仅显示自由OH伸缩振动（νπOH）。当里德堡态收敛到局部π束缚最小值的振动激发能级时，在MATI-IR光谱中除了观察到νπOH外，还观察到氢键整体最小值的氢键OH伸缩振动（νHOH），即使振动激发仅高于IE 0（π）14 cm−1。这些结果表明，Ar配体从芳香环到OH基团的π → H位点转换反应仅从π结合阳离子核中的振动激发态进行，其距离IE 0（π）小于14 cm−1的小势垒。另一方面，直接光电离的PhOH+-Ar在IR光谱中显示出νHOH和νπOH，即使当它刚刚电离到IE 0（π）时。这一结果意味着，电离诱导的π → H位转换发生在H结合或π结合阳离子中没有多余的能量，与非常高的n里德堡态收敛到π结合阳离子的能级相反。Rydberg离子核和裸离子的位置转换效率的不同以及π → H位置转换的机制，除了传统的垂直电离和高n Rydberg态的跃迁外，还通过从π束缚到H束缚结构的直接电离来解释。
The structure of the phenol–argon cluster (PhOH–Ar) in high-n Rydberg states is investigated by the newly developed technique of mass analyzed threshold ionization detected infrared (MATI-IR) spectroscopy. This method selectively measures IR spectra of molecular clusters in very high-n Rydberg states (n > 100) utilized in zero kinetic energy (ZEKE) photoelectron and MATI spectroscopy, whose ionic cores are essentially the same as the corresponding bare cation. The MATI-IR spectrum exhibits only the free OH stretching vibration (νπOH) when the π-bound cluster of the neutral ground electronic state (S0) is resonantly excited via the S1 origin to Rydberg states converging to its adiabatic ionization energy level, IE0(π). When Rydberg states converging to vibrationally excited levels of the local π-bound minimum are prepared, in addition to νπOH also the hydrogen-bonded OH stretching vibration (νHOH) of the H-bonded global minimum is observed in the MATI-IR spectra, even for vibrational excitation of only 14 cm−1 above IE0(π). These results show that the π → H site switching reaction of the Ar ligand from the aromatic ring to the OH group proceeds only from vibrationally excited states in the π-bound cation core with a small barrier of less than 14 cm−1 from IE0(π). On the other hand, directly photoionized PhOH+–Ar shows both νHOH and νπOH in the IR spectra, even when it is just ionized to IE0(π). This result implies that the ionization-induced π → H site switching occurs without excess energy in the H-bound or π-bound cations, in contrast to very high-n Rydberg states converging to levels of the π-bound cation. The different efficiencies of the site switching for the Rydberg ion core and the bare ion and the mechanism for the π → H site switching are interpreted by direct ionization from the π-bound to the H-bound structures in addition to the conventional vertical ionization and transitions to high-n Rydberg states.
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S(0) 和 S(1) 态的苯酚-Ar(n) (n=1,2) 簇的结构。
DOI：
10.1063/1.3149780
发表时间：
2009
期刊：
The Journal of chemical physics
影响因子：
--
作者：
I. Kalkman;C. Brand;Thi Bao Chau Vu;W. Meerts;Y. Svartsov;O. Dopfer;X. Tong;K. Müller;S. Grimme;M. Schmitt
通讯作者：
M. Schmitt
在苯酚·Ar络合物上展示的同步、高分辨率ZEKE和MATI光谱的新检测方案
影响因子：
2.8
作者：
C. Dessent;S. Haines;K. Müller
通讯作者：
K. Müller
苯−H2O团簇电离过程的动力学：直接从头算动力学研究
影响因子：
2.9
作者：
H. Tachikawa;Manabu Igarashi
通讯作者：
Manabu Igarashi
苯酚+–Krn簇阳离子（n = 1,2）的红外光谱：光电离诱导π→H异构化的证据
DOI：
--
发表时间：
2007
期刊：
影响因子：
--
作者：
A. Patzer;J. Langer;Harald Knorke;Helge Neitsch;O. Dopfer;M. Miyazaki;Kaori Hattori;Akihiro Takeda;S. Ishiuchi;M. Fujii
通讯作者：
M. Fujii
影响因子：
2.8
作者：
J. Bardsley
通讯作者：
J. Bardsley