Thomas J. Preston, Maitreya Dutta, Brian J. Esselman, Michael A. Shaloski, Robert J. M C Mahon, and F. Fleming Crim UW-Madison Aimable Kalume, Lisa George,

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Presentation transcript:

Thomas J. Preston, Maitreya Dutta, Brian J. Esselman, Michael A. Shaloski, Robert J. M C Mahon, and F. Fleming Crim UW-Madison Aimable Kalume, Lisa George, and Scott A. Reid University of Marquette Isomerization Between CH 2 ClI and CH 2 Cl-I in Cryogenic Matrices Studied on Ultrafast Timescales

Isomerization of Halomethanes First identified in solid matrices with frequency-domain spectroscopy* Return to parent following electronic excitation Stable in cryogenic solids Transient in liquids *Maier…Hess, JACS, 112, 5117 (1990).

Experiment Frequency DomainTime Domain 500:1 Pulsed deposition Tunable, Nd:YAG nanosecond dye laser Static, difference spectroscopy 220:1 Continuous deposition Ultrafast, Ti:Sapphire laser Transient absorption spectroscopy

Potential Energy Sketch

Transient Absorption - Photolysis

Transient Absorption - Probe

Transient Absorption - Recovery

Spectroscopy of Parent and Isomer

Pump and Probe Wavelengths

Probe Vibrational Energy with Electronic Transition

Isomer Absorption In Ar, N 2, CH 4

Transient Absorption: CH 4

Rise time,  1 / ps 1.1(2) 1.4(1) 2.3(3) 3.1(3)

Transient Absorption: CH 4 Rise or fall time,  2 / ps 42(7) 276(122) 49(13) 37(5)

Potential – 1D

Isomer Formation and Relaxation  1 : 1 ps  2 : 40 ps MP2/Sadlej-pVTZ

Trends Same in CH 4, N 2, and Ar

Complete Picture Vibrationally excited isomer forms in about 1 ps Vibrational relaxation occurs in about 40 ps Both of these timescales are similar in liquid and super-critical fluids

Unanswered Questions What is the detailed process of formation (  1 )? Formation time is 2x faster in N 2 and CH 4 than in Ar What is the detailed process of cooling (  2 )? Rates are indiscriminate of matrix complexity Rates similar among solids, liquids, super-critical fluids Opportunity for MD simulations

Acknowledgements Scott Reid and group at Marquette Static spectroscopy Calculations Bob McMahon and group at UW-Madison Matrix isolation apparatus Calculations Fleming Crim and group at UW-Madison

End of slide show, click to exit.

Thomas J. Preston, Maitreya Dutta, Brian J. Esselman, Michael A. Shaloski, Robert J. McMahon, and F. Fleming Crim UW-Madison Aimable Kalume, Lisa George, and Scott A. Reid University of Marquette Isomerization of CH 2 Cl-I to CH 2 ClI in Cryogenic Matrices: A Study on Ultrafast Timescale

Recap: Formation of the Isomer

Explore Potential Energy Surface a

Setup Probe Preparation Pump Destruction Wall-Clock Time Isomer Population

Probe Isomer or Parent?

Prep. Pump Probe

Destruction of Isomer pump = 400 nm probe = 400 nm pump = 800 nm probe = 400 nm

IR Pump – C-H Stretch Overtone Loss to Parent Vibrational Relaxation 6000 cm -1

IR Pump – C-H Stretch Fundamental 3000 cm -1 Vibrational Relaxation

Vibrational Relaxation

Excite C-H stretch Energy flows into Franck-Condon mode (  1 ) Energy flows into surroundings (  2 )

Infrared Excitation 100  m-thick samples 10-20% conversion to isomer Small absorption at C-H overtone Exceptionally large cross section at C-H fundamental

Acknowledgements Scott Reid and group at Marquette Static spectroscopy Calculations Bob McMahon and group at UW-Madison Matrix isolation apparatus Calculations Fleming Crim and group at UW-Madison