Research at a Liberal Arts College Make sure

Research at a Liberal Arts College Make sure you have a net for your high wire act Mark D. Marshall Helen O. Leung Department of Chemistry Amherst College

Research at a liberal arts college n An expectation for accomplishment in both teaching and research n n A big selling point for some of us Different interpretations at different institutions n Undergraduate involvement n n n Required in all projects Offer opportunities for significant participation Collaborations n n Discouraged Encouraged

Challenges – outside the lab n n n Limited start-up funds Laboratory infrastructure Teaching responsibility – lectures, laboratory, and grading duties take big chunks of time n n Classroom contact hours – 11 -15 hours/week at a minimum Office hours – 3 or more hours/week expected plus individual appointments No course relief for supervising research students Committee service

Challenges – inside the lab n n Limited, if any, machine shop/electronic shop support from College No continuity from student to student n n n Students typically work in the summer and/or short hours during academic year Must provide repeated, individual training for using instrumentation and in learning spectroscopy Students spend a limited amount of time in lab n Cannot rely on students to do maintenance

Strategies for success n n Need instrument that is easy to maintain Find niches Devise student projects that are not too involved and that produce results fairly quickly. Make effective use of opportunities

Fourier transform microwave spectrometer n n First year was spent mostly in writing external grants and designing spectrometer First generation spectrometer was brought into operation with used/borrowed vacuum and microwave components. After a second and third round of grants, spectrometer was finally sensitive enough to study intermolecular complexes. Chirped pulse FTMW spectroscopy brings even more advantages

Strategies for success n n Need instrument that is easy to maintain Find niches Devise student projects that are not too involved and that produce results fairly quickly. Make effective use of opportunities

N 2 O-containing complexes • • • Not extensively studied in the microwave Two quadrupolar 14 N nuclei in N 2 O make the resolution and assignment of spectral lines formidable – expected little competition! Population in each rotational level is divided into many sublevels – weak transition lines Complicated spectrum gives valuable information on intermolecular forces Study made possible by computing power and FTMW spectroscopy

Complexes studied • Ar-N 2 O • • • CO 2 -N 2 O • • • HCCH-14 N 2 O HCCH-15 N 14 NO CO 2 -14 N 2 O CO 2 -15 N 14 NO N 2 -N 2 O • 15 N -14 N O 2 2 OCS-N 2 O • Ar-14 N 2 O • HCCH-N 2 O • • • OC 32 S-14 N 2 O OC 32 S-15 N 14 NO OC 32 S-15 N 2 O OC 34 S-15 N 2 O HF-N 2 O • • • HF-14 N 2 O HF-15 N 14 NO HF-15 N 2 O DF-14 N 2 O DF-15 N 14 NO DF-15 N 2 O • HCl-N 2 O • • • H 35 Cl-14 N 2 O H 37 Cl-14 N 2 O H 35 Cl-15 N 14 NO H 35 Cl-15 N 2 O D 35 Cl-15 N 2 O Electric field gradient perturbation has been observed in all but two species: OCS-N 2 O and the linear isomer of HF-N 2 O.

Haloethylene complexes • • • Recent work focuses on complexes containing halosubstituted ethylenes. An increase in the number of F substituents has significant effects on the nature of intermolecular interactions. Can fine tune the properties of the functional groups to observe how they compete or cooperate with each other.

Empirical rules: Legon & Millen Planar or near planar • H bond: § HX lies along a ^ bisector of a p bond § In the presence of a lone pair, HX lies along the axis of the lone pair • Bend in H bond is caused by a secondary interaction between X and H in vinyl fluoride

Vinyl fluoride-HX Vinyl fluoride-HCCHa • j = 122. 6(4)o • q = 36. 5(2)o • RH-F = 2. 441 Å Vinyl fluoride-HClb • j = 123. 7(1)o • q = 18. 3(1)o • RH-F = 2. 123(1) Å a. Cole and Legon, CPL 369, 31(2003) b. Kisiel, Fowler, and Legon, JCP 93, 3054 (1990); Legon and Ottaviani, PCCP 4, 4103 (2002)

Selected examples

The strange case of vinyl chloride

Strategies for success n n Need instrument that is easy to maintain Find niches Devise student projects that are not too involved and that produce results fairly quickly. Make effective use of opportunities

Freedom to throw money at things n n Faculty time is the most valuable resource. Expertise may not be in-house: look outside. Commercial solution is likely to be better and will certainly be quicker. Think of all the money saved by not having to support graduate students!

Effective use of sabbaticals n Go and hide in your own lab n n Focused, uninterrupted work by an expert Go and hide in someone else’s lab n Focused, uninterrupted work with another expert

Sabbaticals spent elsewhere UNC-Chapel Hill: 1990 -1991 Propensity rules and vector correlations in predissociation of weakly bound complexes Six papers University of Rochester: 1995 -1996 Dipole moments in excited vibrational states Three papers University of Pennsylvania: 2000 -2001 Vibrational spectroscopy of open shell complexes Four papers University of Pennsylvania: 2003 -2004 Quenching of orbital angular momentum in open shell complexes Four papers

Forge effective collaborations Three papers before 1995 -96 sabbatical, one after (plus two as an undergraduate) One paper and one collaborative facility NSF grant Three papers plus one in preparation One paper since sabbaticals there Suggested new collaboration leading to recent paper Three papers after post-doc 21 papers, four NSF grants, and much more

Forge effective collaborations Source of much microwave and vacuum equipment (and advice). Implementation and installation of FTMW spectrometer upgrade Access to top quality machine shop and loaner vacuum pump One paper and sage advice Two papers plus one in preparation 21 papers, four NSF grants, and much more

Emerging collaborations NO 2 Dimer Formic Acid – Acetic Acid

Chirped pulse advice

Undergraduate research students: His James Kim ‘ 90 Sabah Servaes ‘ 90 Brian Bean ‘ 94 Tom Cameron (Cornell Univ. ) Keya Khayatain ‘ 94 Karl Lee ‘ 94 Jessica Wolpaw ’ 94 Robert Friday ‘ 94 Alex de Winter ‘ 95 Andrea Dutton ‘ 95 Morgan Mc. Kenny ’ 95 Monish Bhatia ‘ 96 Aaron Schuster ‘ 96 Ken Solt ‘ 96 Eliot Deloach ‘ 96 Janina Matuszeski ‘ 97 Bryan Winn ‘ 97 Marnie O’Brien ‘ 98 Giora Proskuroski ‘ 98 Dana Bae ‘ 00 Debbie Chang ‘ 00 Jared Cross ‘ 00 Koon-Cheung Ching ‘ 02 Michael Dougan ‘ 02 Phuc Pho ‘ 02 Sebastian Cruz-Schiavone ‘ 03 Christine Hagan ‘ 05

Undergraduate research students: Hers David Moore '92 Rochelle Torgerson '92 Allison Meade '93 David Young '93 Madeleine Martindale 'FP Vidya Prasad '95 Tania Mahajan '96 Deepa Gangwani '96 Botol Maqsodi '97 Sarah Cureton '97 Hai Dang Nguyen '99 Jelena Antonic '99 Sarah Butkus '01 Areeya Vimayangoon '01 Ruvini Samaranayake '01 Anne Osowski '01 Roxane Shafaee-Moghadam '01 Olayinka Oyeyemi '00 Patricia Abrũna '02 Mary Bianchi '02 Oluwatoyin Ibidapo '02 Sujin Joo '04 Winn Cashion '05 Christine Hagan '05 Katharine Duncan '06 Jasmina Cheung-Lau '07

Undergraduate research students: Ours Ryan Welch '03 Charlene Hawkins '06 Brent Amberger '08 Vincent Chen '08 Justin Kang '08 Margaret Ray '08 Nazir Savji '08 Andrew Vasta '08 Catherine Calvert '09 Tasha Drake '09 David Grimes '09 Alex Lee '09 Tadeusz Pudlik '09 Daniel Mc. Cune '09 Jonathan Tucker '09 Aaron Bozzi '10 Mary Beth Broadbent '10 Paul Cohen '10 Lucy Yao '10 Jenny Cook-Kollars '11 Cynthia Chio '12 Edmund Keyes '12 Benjamin Scheetz '12 Jonathan Thaler '12 Mable Lam '12 Jessica Mueller '13 Joseph Messenger '14 Eli Mlaver '14 Allan Landman '14 Nazir Khan '15 Gregory Knowlton '15 Gillian Lupinski '15 Katherine Sundheim '15 Jimmy Yu '15 Mark Boyer '16 Ilya Kiselev '16 Hannah Tandon '16 Jesse Fajnzylber '17 Kimberly Greenberg '17 Craig Nelson '18 Leonard Yoon '18 And more on the way…

How can we visualize the safety net? The community of spectroscopists! Brought together each year at ISMS