Frontiers and Advances in Molecular Spectroscopy

Jaan Laane

• Publisher: Elsevier Science
• Year: 2017
• Print ISBN: 9780128112205
• eBook ISBN: 9780128112212
• Topic: Naturwissenschaften
• Subtopic: Analytische Chemie

Frontiers and Advances in Molecular Spectroscopy once again brings together the most eminent scientists from around the world to describe their work at the cutting-edge of molecular spectroscopy. Much of what we know about atoms, molecules and the nature of matter has been obtained using spectroscopy over the last one hundred years or so. Going far beyond the topics discussed in Jaan Laane's earlier book on the subject, these chapters describe new methodologies and applications, instrumental developments and theory, which are taking spectroscopy into still new frontiers. The robust range of topics once again demonstrates the wide utility of spectroscopic techniques. New topics include ultrafast spectroscopy of the transition state, SERS/far-uv spectroscopy, femtosecond coherent anti-Stokes Raman spectroscopy, high-resolution laser induced fluorescence spectroscopy, Raman spectroscopy and biosensors, vibrational optical activity, ultrafast two-dimensional spectroscopy, biology with x-ray lasers, isomerization dynamics and hydrogen bonding, single molecule imaging, spectra of intermediates, matrix isolation spectroscopy and more. - Covers spectroscopic investigations on the cutting edge of science - Written and edited by leading experts in their respective fields - Allows researchers to access a broad range of essential modern spectroscopy content from a single source rather than wading through hundreds of scattered journal articles

Chapter 1

Stark-Induced Adiabatic Passage Processes to Selectively Prepare Vibrationally Excited Single and Superposition of Quantum States

Nandini Mukherjee; William E. Perreault; Richard N. Zare Stanford University, Stanford, CA, United States

Abstract

We describe Stark-induced adiabatic Raman passage (SARP), a technique that we have extensively developed in our laboratory to prepare vibrationally excited single and superposition of quantum states of molecules with a large population density in a collision-free ambience, such as in a molecular beam. We present a theoretical framework of SARP using Schrödinger and density matrix equations. A Bloch-Feynman vector model picture is constructed to provide an intuitive and pictorial description of the Stark-induced adiabatic population transfer. Experimental results are presented in support of our theoretical simulations of SARP preparing both single and superpositions of rovibrational M-quantum states with near-complete population transfer. Additionally, we introduce a new Stark-induced adiabatic ladder climbing technique that is able to selectively populate a high-lying vibrational quantum state near dissociation. Brief descriptions of other related adiabatic passage processes, such as stimulated Raman adiabatic passage (STIRAP) and Stark-chirped rapid adiabatic passage (SCRAP), are added for completeness and for comparison with SARP.

Keywords

Adiabatic passage; Stark chirping; Vibrational excitation; Stimulated Raman

Chapter Outline

1. Introduction

1.1 How Can a Large Ensemble of Molecular Targets be Prepared in a Selected Highly Vibrationally Excited Quantum State With Rotational (J, M) Quantum Number Precision?

2. Theory of Stark-Induced Adiabatic Raman Passage

2.1 Schrödinger Equation for Stimulated Raman Pumping

2.2 Density Matrix Equation

2.3 Saturation of Raman Pumping in a High-Pressure Gas Cell

2.4 Bloch Vector Model for Stark-Induced Adiabatic Passage

2.5 Rabi Oscillations

2.6 Coherent Population Return is a Problem for Stark-Induced Population Transfer

2.7 How Do We Accomplish Stark-Induced Adiabatic Passage Using Pulsed Excitation?

3. Theoretical Simulation of SARP for H₂ v = 0 → v = 1 Transitions

3.1 SARP is a Threshold Phenomenon

4. Experimental Demonstration of SARP Preparing Single and Superpositions of Quantum States

4.1 Preparation of a Bi-Axial Superposition State Within a Single Rovibrational H₂ (v = 1, J = 2) Eigenstate

4.2 Demonstration That SARP is a Robust Technique for Preparing a Desired Rovibrational M-Quantum State

5. SARP Excitation of a High Vibrational (v = 4) Level

6. Vibrational Ladder Climbing Using Multicolor SARP

6.1 How Do We Prepare A Diatomic Molecule in An Arbitrary High Vibrational Level?

6.2 Theory of Four-Photon Three-Color SARP

6.3 Vibrational Ladder Climbing of H₂ Using Three-Color SARP

6.4 Preparation of H₂ (v = 6, J = 0) Using Three-Color SARP

6.5 Preparation of a Pair o...

Table of contents

• Cover image
• Title page
• Table of Contents
• Copyright
• Contributors
• Preface
• Chapter 1: Stark-Induced Adiabatic Passage Processes to Selectively Prepare Vibrationally Excited Single and Superposition of Quantum States
• Chapter 2: Advances in Two-Dimensional Correlation Spectroscopy (2DCOS)
• Chapter 3: Applications of 2D-IR Spectroscopy to Probe the Structural Dynamics of DNA
• Chapter 4: Vibrational Potential Energy Surfaces in Ground and Excited Electronic States
• Chapter 5: Structures and Dipole Moments of Molecules in Their Electronically Excited States
• Chapter 6: Two-Color Pulsed-Field Ionization-Photoelectron Spectroscopy: A Quest to Benchmark State-of-the-Art ab initio Quantum Electronic Structure Calculations of Spectroscopic and Energetic Properties for Transition Metal-Containing Species
• Chapter 7: Advances in Far-Ultraviolet Spectroscopy in the Solid and Liquid States
• Chapter 8: Development of Sub-10 fs Visible-NIR, UV, and DUV Pulses and Their Applications to Ultrafast Spectroscopy
• Chapter 9: Biomedical Applications of Surface-Enhanced Raman Scattering Spectroscopy
• Chapter 10: SERS Biomedical Applications: Diagnostics, Forensics, and Metabolomics
• Chapter 11: Quantitative Spectrometry of Complex Molecular Systems by Hypothetical Addition Multivariate Analysis With Numerical Differentiation (HAMAND)
• Chapter 12: Progress in FAST CARS Toward Quantum Biophotonics
• Chapter 13: Coherent Raman Generation in Solid-State Materials Using Spatial and Temporal Laser Field Shaping
• Chapter 14: Vibrational Optical Activity: From Small Chiral Molecules to Protein Pharmaceuticals and Beyond
• Chapter 15: High-Resolution Laboratory Terahertz Spectroscopy and Applications to Astrophysics
• Chapter 16: Studying Interaction, Ion-Pair Formation, and Mixing Behavior of Protic Ionic Liquids by Means of Far-Infrared Spectroscopy
• Chapter 17: Advancements in Microwave Spectroscopy
• Chapter 18: Nitric Oxide Laser-Induced Fluorescence Imaging Methods and Their Application to Study High-Speed Flows
• Chapter 19: Photogeneration of Rare Molecules in Cryogenic Matrices: Spectroscopists' Adventures in Wonderland
• Chapter 20: Matrix Isolation Spectroscopic Studies: Thermal and Soft Photochemical Bimolecular Reactions
• Chapter 21: Theory of Enantiomer-Specific Microwave Spectroscopy
• Index