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<!--StartFragment--><p class="MsoTitle" style="text-align: center; margin-right: -0.5in;"><b><span style="font-family: 'Times New Roman'; font-size: 14px;">Seminar on</span></b></p><p class="MsoNormal" align="center" style="text-align:center"><span style="font-size: 14px;"><b><span style="letter-spacing: 1.5pt;">Modern Optics and Spectroscopy</span></b></span></p><p class="MsoNormal" align="center" style="text-align:center"><b><span style="font-family: Arial; letter-spacing: 1pt; font-size: 14px;"> </span></b></p><p class="MsoNormal" align="center" style="text-align:center"><b><i><span style="letter-spacing: 1pt; font-size: 14px;">Optical rotatory dispersion: </span></i></b><b><i><span style="letter-spacing: 1pt; font-size: 14px;">New twists on and old topic</span></i></b></p><p class="MsoNormal" align="center" style="text-align:center"><b><i><span style="letter-spacing: 1pt; font-size: 14px;"> </span></i></b></p><p class="MsoNormal" align="center" style="text-align:center"><b><span style="letter-spacing: 1pt; font-size: 14px;">Patrick Vaccaro,<o:p></o:p></span></b></p><p class="MsoNormal" align="center" style="text-align:center"><span style="letter-spacing: 1pt; font-size: 14px;">Yale
University</span></p><p class="MsoNormal" align="center" style="text-align:center"><span style="letter-spacing: 1pt; font-size: 14px;">Tuesday,
May 5, 2015<o:p></o:p></span></p><p class="MsoNormal" align="center" style="text-align:center"><span style="letter-spacing: 1pt;"><span style="font-size: 14px;">12:00 –
1:00 p.m.</span><font size="6"><o:p></o:p></font></span></p><div style="margin: 0in 0in 0.0001pt; text-align: justify;"><span style="font-size: 14px;"><span style="font-family: Helvetica;">Among the many physiochemical properties that
distinguish chiral molecules, perhaps none has had as profound and sustained an
impact on chemistry as the characteristic interactions taking place with
polarized light. Of special note is the dispersive (non-resonant) phenomenon of
circular birefringence (CB), the manifestation of which first was reported over
two centuries ago and which still is used routinely (in the more familiar guise
of specific optical rotation) to gauge the enantiomeric purity of asymmetric
syntheses. Ongoing efforts to probe such electronic optical activity in <i>isolated</i>
chiral molecules will be presented, with special emphasis directed towards the
marked influence that intramolecular (vibrational/conformational) dynamics and
intermolecular (environmental) perturbations can exert upon the intrinsic
response. Requisite isolated-molecule measurements have been made possible by
our continuing development of cavity ring-down polarimetry (CRDP), an
ultrasensitive polarimetric scheme that has permitted the first quantitative
analyses of optical rotatory dispersion (or wavelength-resolved CB) to be
performed in rarefied media. Various technical aspects of CRDP will be
discussed to illustrate the unique capabilities and practical limitations
afforded by this approach. Comparison of specific rotation values acquired for
diverse rigid and flexible species under complementary isolated and solvated
conditions will demonstrate the pronounced, yet oftentimes counterintuitive,
effects incurred by the coupling among solute and solvent degrees of freedom.
The disparate nature of optical activity in different environments will be
highlighted, with quantum-chemical calculations serving to elucidate the
structural and electronic provenance of observed behavior. Aside from
unraveling processes that mediate chiroptical response in condensed media, the
resulting vapor-phase information affords a critical assessment for theoretical
predictions of electronic optical activity and for their emerging ability to
assist in the determination of absolute stereochemical configuration.</span><span style="line-height: 115%; font-family: 'Times New Roman';"><o:p></o:p></span></span></div><div style="margin: 0in 0in 0.0001pt; text-align: justify;"><span style="line-height: 115%; font-family: 'Times New Roman'; font-size: 14px;"><o:p> </o:p></span><span style="font-size: 14px;"> </span></div><p class="MsoNormal" align="center" style="text-align:center"><span style="font-size: 14px;">Grier Room, MIT Bldg. 34-401<o:p></o:p></span></p><p class="MsoNormal" align="center" style="text-align:center">
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<!--EndFragment--></p><p class="MsoNormal" align="center" style="text-align:center"><span style="font-size: 14px;">Refreshments served after the lecture</span><span style="font-size: 16pt;"><o:p></o:p></span></p>
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