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Lett."},{"key":"ref22\/cit22","unstructured":"Benzler, J.Ph.D. Thesis, University of G\u00f6ttingen, 1997."},{"key":"ref23\/cit23","doi-asserted-by":"crossref","first-page":"2180","DOI":"10.1039\/b720037d","volume":"10","author":"Stalke S.","year":"2008","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref24\/cit24","doi-asserted-by":"crossref","first-page":"948","DOI":"10.1007\/s11172-005-0339-8","volume":"54","author":"Semikolenov S. V.","year":"2005","journal-title":"Russ. Chem. Bull."},{"key":"ref25\/cit25","doi-asserted-by":"crossref","first-page":"911","DOI":"10.1016\/S0040-4020(01)80333-1","volume":"49","author":"Mordi R. C.","year":"1993","journal-title":"Tetrahedron"},{"key":"ref26\/cit26","doi-asserted-by":"crossref","first-page":"10296","DOI":"10.1021\/jp010022n","volume":"105","author":"Zigmantas D.","year":"2001","journal-title":"J. Phys. Chem. 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B"},{"key":"ref28\/cit28","unstructured":"For this, a minor rescaling of the relative signal amplitudes of the measurements at parallel and perpendicular configurations was necessary, due to slightly different experimental conditions, i.e., overlap of the two beams as well as pulse energies when rotating the polarizer."},{"key":"ref29\/cit29","doi-asserted-by":"crossref","first-page":"743","DOI":"10.1016\/S0378-3812(99)00100-4","volume":"158","author":"Tuma D.","year":"1999","journal-title":"Fluid Phase Equilib."},{"key":"ref30\/cit30","unstructured":"Tuma, D.Ph.D. Thesis, Ruhr University Bochum, 1999."},{"key":"ref31\/cit31","doi-asserted-by":"crossref","first-page":"549","DOI":"10.1007\/BF02268278","volume":"39","author":"Hui B.","year":"1994","journal-title":"Chromatographia"},{"key":"ref32\/cit32","doi-asserted-by":"crossref","first-page":"274","DOI":"10.1016\/0896-8446(92)90019-G","volume":"5","author":"Jay A. J.","year":"1992","journal-title":"J. Supercrit. Fluids"},{"key":"ref33\/cit33","doi-asserted-by":"crossref","first-page":"4569","DOI":"10.1021\/jp000079u","volume":"104","author":"Frank H. A.","year":"2000","journal-title":"J. Phys. Chem. B"},{"key":"ref34\/cit34","doi-asserted-by":"crossref","first-page":"8052","DOI":"10.1021\/jp022648z","volume":"107","author":"Shima S.","year":"2003","journal-title":"J. Phys. Chem. A"},{"key":"ref35\/cit35","doi-asserted-by":"crossref","first-page":"5339","DOI":"10.1021\/jp0272318","volume":"107","author":"Zigmantas D.","year":"2003","journal-title":"J. Phys. Chem. B"},{"key":"ref36\/cit36","unstructured":"For 12\u2032C in scCO2, the change of temperature over 308\u2212332 K at constant density (reduced density\u03c1r=\u03c1\/\u03c1c= 1.36) resulted in a small shift of 164 cm\u22121(\u22122.5 nm) (seeSupporting Information Table S1(e)). Almost no thermochromic shift was observed for 12\u2032C in scCF3H over the temperature range 308\u2212333 K at constant density (\u03c1r= 1.70, seeSupporting Information Table S1(h)). In the case of 8\u2032C, thermochromic shifts of 224 cm\u22121(\u22124.1 nm) in scCO2over the temperature range 309\u2212333 K at the constant density\u03c1r= 1.29 (seeSupporting Information Table S2(e)) and of 220 cm\u22121(\u22124.2 nm) in scCF3H at the constant density\u03c1r= 1.70 over the temperature range 308\u2212334 K (seeSupporting Information Table S2(h)) were observed."},{"key":"ref37\/cit37","doi-asserted-by":"crossref","first-page":"7096","DOI":"10.1021\/jp0206727","volume":"106","author":"Patel N.","year":"2002","journal-title":"J. Phys. Chem. B"},{"key":"ref38\/cit38","doi-asserted-by":"crossref","first-page":"6924","DOI":"10.1021\/jp000888d","volume":"104","author":"Song W.","year":"2000","journal-title":"J. Phys. Chem. A"},{"key":"ref39\/cit39","doi-asserted-by":"crossref","first-page":"3009","DOI":"10.1039\/B315786E","volume":"6","author":"Zigmantas D.","year":"2004","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref40\/cit40","doi-asserted-by":"crossref","first-page":"3758","DOI":"10.1002\/anie.200604762","volume":"46","author":"P\u00e9rez Lustres J. L.","year":"2007","journal-title":"Angew. Chem., Int. Ed."},{"key":"ref41\/cit41","doi-asserted-by":"crossref","first-page":"19","DOI":"10.1016\/0301-0104(78)87022-0","volume":"31","author":"Reinartz J. M. L. J.","year":"1978","journal-title":"Chem. Phys."},{"key":"ref42\/cit42","doi-asserted-by":"crossref","first-page":"1521","DOI":"10.1021\/jp044847j","volume":"109","author":"Billsten H. H.","year":"2005","journal-title":"J. Phys. Chem. A"},{"key":"ref43\/cit43","doi-asserted-by":"crossref","first-page":"834","DOI":"10.1021\/bi00842a042","volume":"7","author":"Buchwald M.","year":"1968","journal-title":"Biochemistry"},{"key":"ref44\/cit44","doi-asserted-by":"crossref","first-page":"680","DOI":"10.1002\/chir.10282","volume":"15","author":"Simonyi M.","year":"2003","journal-title":"Chirality"},{"key":"ref45\/cit45","unstructured":"A separation into two distinct populations might appear artificial from a physical standpoint and partly stems from the suggestive nature of the biexponential fit of the decay. We note that the decay of the transient absorption profiles in CF3H could also be well described by using a \u201cstretched-exponential\u201d term instead of the first two exponential terms in eq7, leading toI(t) = (A0+A1\u2009exp{\u2212[(t\u2009\u2212t0)\/\u03c41]Y} +A3\u2009exp{\u2212(t\u2009\u2212t0)\/\u03c43})\u00b70.5(1 + erf{(t\u2009\u2212t0)\/(\u221a2\u03c3)}). Here, the parameterY(<1) in the first term merely describes the departure from monoexponential behavior. Such an approach (requiring one parameter less than eq7) has been frequently used in the absence of a theoretical model to describe the relaxation of solute molecules, which are sampling different types of microenvironments within a solvent [Arzhantsev et al.J. Phys. Chem. B2007,111, 4978; Ingram et al.J. Phys. Chem. B2003,107, 5926]. Using the equation above, one obtains, e.g., in scCF3H at 308 K (\u03bbprobe= 545 nm) at 90 bar,\u03c41= 29.9 ps,\u03911= 83%,Y= 0.651,\u03c43= 1.0 ps, andA3= \u221217%, and at 300 bar,\u03c41= 13.5 ps,\u03911= 72%,Y= 0.674,\u03c43= 0.6 ps, andA3= \u221228% (compare the values inSupporting Information Table S3). Note that the parameterYdescribing the stretched-exponential character of the relaxation is very similar at both pressures, emphasizing that only the overall time scale of the relaxation but not its character is changing."},{"key":"ref46\/cit46","doi-asserted-by":"crossref","first-page":"2369","DOI":"10.1103\/PhysRevA.59.2369","volume":"59","author":"Kovalenko S. A.","year":"1999","journal-title":"Phys. Rev. A"},{"key":"ref47\/cit47","volume-title":"Gaussian 03","author":"Frisch M. J.","year":"2003"},{"key":"ref48\/cit48","unstructured":"Schwarzer, D.Ph.D. Thesis, University of G\u00f6ttingen, 1989."},{"key":"ref49\/cit49","doi-asserted-by":"crossref","first-page":"9867","DOI":"10.1063\/1.1514570","volume":"117","author":"Kiyohara K.","year":"2002","journal-title":"J. Chem. Phys."},{"key":"ref50\/cit50","doi-asserted-by":"crossref","first-page":"8653","DOI":"10.1063\/1.478773","volume":"110","author":"Bartolini P.","year":"1999","journal-title":"J. Chem. 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