Prof. Robert W Field

Robert T Haslam and Bradley Dewey Professor of Chemistry
Associate Director, Spectroscopy Laboratory

Primary DLC

Department of Chemistry

MIT Room: 6-219


Peter Giunta

Areas of Interest and Expertise

Physical Chemistry
Tunable Lasers
Rates, Barriers to, and Mechanisms of Intramolecular Vibrational Energy Redistribution (IVR)
Electronic Structure of Diatomic Molecules
Structure/Dynamics of Vibrationally Excited Polyatomic Molecules
Optical-Optical Double Resonance Spectrscopy (OODR)
Stimulated Emission Pumping (SEP)
Electronic Structure of Transition Metal Hydrides and Halides
Development of New Molecular Sources for Laser Spectroscopy
Computer-Automated Spectrum Assignment and Pattern Recognition
Advanced Pattern Recognition Techniques
Novel Sources for Transient Molecules
Sensitive and Selective Laser Diagnostics for Free Radical and High Temperature Species
Spectroscopy of Metastable Electronic Statres of Small Molecules
InterSystem Crossing

Research Summary

Polyatomic molecules are like balls-and springs, yet eigenstates are stationary. Where has the intricate and beautiful dance of atoms gone and how do we recover movies of intramolecular dynamics from complicated line-spectra that are recorded in the frequency-domain? Is Intramolecular Vibrational Redistribution (IVR) a code for "I really don't know what is going on" or is it an explainable, cause-and-effect mechanistic process: where does the initially localized energy flow, how fast, and why? A complete description is like a telephone directory, true but unmemorable. Mechanism is insight, even if it is neither as true nor complete as a telephone directory.

How does an electron exchange energy and angular momentum with vastly more massive nuclei? Frequency- and time-domain spectra of Rydberg states can reveal the fundamental mechanisms of electron—nuclear interactions, provided that we learn how to recognize and interpret the characteristic patterns of these simple interactions rather than the more traditional but opaque state-by-state multi-digit molecular constants. When the periods of classical mechanical motions of electrons and nuclei are equal, "resonance" occurs and energy flow is rapid. How is resonance encoded in a spectrum? Can we design experiments to be explicitly sensitive to resonance or to use resonance for rational external control of intramolecular dynamics?

In Freshman Chemistry we teach/learn about the periodic table, and simple ideas about atomic electronic structure provide elegantly simple explanations for diverse properties of matter. Oxidation states emerge as a descriptive concept capable of making sense of a wide range of chemical and spectroscopic properties of metal-containing molecules. Yet, for metal-containing diatomic and triatomic molecules, both spectroscopists and ab initio quantum chemists seem to have no use for oxidation states. The spectra of these molecules are extremely complicated and understanding them will require unconventional spectroscopic techniques and heretical electronic structure models.

Tunable lasers, often two or three simultaneously, are used in Field's Current Research Group to investigate the structural and dynamical properties of small, gas phase molecules. Textbooks present a misleadingly simple picture of how spectroscopists extract information from spectra (which are never born with assignments attached). New, multiple-laser-based and chirped-pulse millimeter wave techniques are making it possible to decode prohibitively complex appearing spectra. Classical mechanics and pattern recognition are becoming important tools for extracting information from spectra.

Stimulated Emission Pumping (SEP) Pump-and-Dump spectroscopy, a technique invented at MIT, is providing unprecedented insights into the dynamics of small polyatomic molecules with chemically significant amounts of vibration-rotation excitation. Soon we will be able to uncover in a spectrum the same molecular gymnastics that an Organic Chemist envisions when she speaks of "1,2-hydrogen shifts." The quality, quantity, and simplicity of SEP spectra make it possible to exploit new pattern recognition schemes to extract short-time dynamics directly from frequency domain spectra.

Recent Work