Full-dimensional theoretical description of vibrationally resolved valence-shell photoionization of H2O.

IF 2.3 2区 物理与天体物理 Q3 CHEMISTRY, PHYSICAL
Structural Dynamics-Us Pub Date : 2019-09-11 eCollection Date: 2019-09-01 DOI:10.1063/1.5106431
Selma Engin, Jesús González-Vázquez, Gianluigi Grimaldi Maliyar, Aleksandar R Milosavljević, Taishi Ono, Saikat Nandi, Denys Iablonskyi, Kuno Kooser, John D Bozek, Piero Decleva, Edwin Kukk, Kiyoshi Ueda, Fernando Martín
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引用次数: 4

Abstract

We have performed a full-dimensional theoretical study of vibrationally resolved photoelectron emission from the valence shell of the water molecule by using an extension of the static-exchange density functional theory that accounts for ionization as well as for vibrational motion in the symmetric stretching, antisymmetric stretching, and bending modes. At variance with previous studies performed in centrosymmetric molecules, where vibrationally resolved spectra are mostly dominated by the symmetric stretching mode, in the present case, all three modes contribute to the calculated spectra, including intermode couplings. We have found that diffraction of the ejected electron by the various atomic centers is barely visible in the ratios between vibrationally resolved photoelectron spectra corresponding to different vibrational states of the remaining H2O+ cation (the so-called v-ratios), in contrast to the prominent oscillations observed in K-shell ionization of centrosymmetric molecules, including those that only contain hydrogen atoms around the central atoms, e.g., CH4. To validate the conclusions of our work, we have carried out synchrotron radiation experiments at the SOLEIL synchrotron and determined photoelectron spectra and v-ratios for H2O in a wide range of photon energies, from threshold up to 150 eV. The agreement with the theoretical predictions is good.

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H2O振动分辨价壳层光电离的全维理论描述。
我们使用静态交换密度泛函理论的扩展,对水分子价壳层的振动分辨光电子发射进行了全维理论研究,该理论解释了对称拉伸、反对称拉伸和弯曲模式下的电离以及振动运动。与之前在中心对称分子中进行的研究不同,在中心对称的分子中,振动分辨光谱主要由对称拉伸模式主导,在目前的情况下,所有三种模式都有助于计算光谱,包括互调耦合。我们发现,与在中心对称分子的K壳层电离中观察到的显著振荡相反,在与剩余H2O+阳离子的不同振动态相对应的振动分辨光电子能谱之间的比率(所谓的v比率)中,不同原子中心对喷射电子的衍射几乎不可见,包括仅在中心原子周围包含氢原子的那些,例如CH4。为了验证我们的工作结论,我们在SOLEIL同步加速器上进行了同步辐射实验,并确定了H2O在从阈值到150的宽光子能量范围内的光电子光谱和v比 与理论预测的一致性很好。
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来源期刊
Structural Dynamics-Us
Structural Dynamics-Us CHEMISTRY, PHYSICALPHYSICS, ATOMIC, MOLECU-PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
CiteScore
5.50
自引率
3.60%
发文量
24
审稿时长
16 weeks
期刊介绍: Structural Dynamics focuses on the recent developments in experimental and theoretical methods and techniques that allow a visualization of the electronic and geometric structural changes in real time of chemical, biological, and condensed-matter systems. The community of scientists and engineers working on structural dynamics in such diverse systems often use similar instrumentation and methods. The journal welcomes articles dealing with fundamental problems of electronic and structural dynamics that are tackled by new methods, such as: Time-resolved X-ray and electron diffraction and scattering, Coherent diffractive imaging, Time-resolved X-ray spectroscopies (absorption, emission, resonant inelastic scattering, etc.), Time-resolved electron energy loss spectroscopy (EELS) and electron microscopy, Time-resolved photoelectron spectroscopies (UPS, XPS, ARPES, etc.), Multidimensional spectroscopies in the infrared, the visible and the ultraviolet, Nonlinear spectroscopies in the VUV, the soft and the hard X-ray domains, Theory and computational methods and algorithms for the analysis and description of structuraldynamics and their associated experimental signals. These new methods are enabled by new instrumentation, such as: X-ray free electron lasers, which provide flux, coherence, and time resolution, New sources of ultrashort electron pulses, New sources of ultrashort vacuum ultraviolet (VUV) to hard X-ray pulses, such as high-harmonic generation (HHG) sources or plasma-based sources, New sources of ultrashort infrared and terahertz (THz) radiation, New detectors for X-rays and electrons, New sample handling and delivery schemes, New computational capabilities.
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