1887
banner image
No data available.
Please log in to see this content.
You have no subscription access to this content.
No metrics data to plot.
The attempt to load metrics for this article has failed.
The attempt to plot a graph for these metrics has failed.
oa
Simultaneous photon absorption as a probe of molecular interaction and hydrogen-bond cooperativity in liquids
Rent:
Rent this article for
Access full text Article
/content/aip/journal/jcp/127/15/10.1063/1.2779033
1.
1.J. Fahrenfort and J. A. A. Ketelaar, J. Chem. Phys. 22, 1631 (1954).
2.
2.A. Ron and D. F. Hornig, J. Chem. Phys. 39, 1129 (1963).
http://dx.doi.org/10.1063/1.1734368
3.
3.C. Bourdéron and C. Sandorfy, J. Chem. Phys. 59, 2527 (1973).
http://dx.doi.org/10.1063/1.1680368
4.
4.W. A. P. Luck and M. Fritzsche, J. Mol. Struct. 295, 47 (1993).
5.
5.S. P. Velsko and D. W. Oxtoby, J. Chem. Phys. 73, 4883 (1980).
http://dx.doi.org/10.1063/1.440017
6.
6.R. Lamanna, G. Floridi, and S. Cannistraro, Phys. Rev. E 52, 4529 (1995).
http://dx.doi.org/10.1103/PhysRevE.52.4529
7.
7.F. N. Keutsch and R. J. Saykally, Proc. Natl. Acad. Sci. U.S.A. 98, 10533 (2001).
http://dx.doi.org/10.1073/pnas.191266498
8.
8.P. Raiteri, A. Laio, and M. Parrinello, Phys. Rev. Lett. 93, 087801 (2004).
http://dx.doi.org/10.1103/PhysRevLett.93.087801
9.
9.C. J. Benmore and P. A. Egelstaff, J. Phys.: Condens. Matter 8, 9429 (1996).
http://dx.doi.org/10.1088/0953-8984/8/47/040
10.
10.G. Herzberg, Molecular Spectra and Molecular Structure II. Infrared and Raman Spectra of Polyatomic Molecules (Van Nostrand Reinhold, New York, 1945).
11.
11.H. Torii, J. Phys. Chem. A 110, 9469 (2006).
http://dx.doi.org/10.1021/jp062033s
12.
12.A. C. Belch and S. A. Rice, J. Chem. Phys. 78, 4817 (1983).
http://dx.doi.org/10.1063/1.445416
13.
13.S. Woutersen and H. J. Bakker, Nature (London) 403, 507 (1999).
14.
14.P. Hamm, M. Lim, W. F. DeGrado, and R. M. Hochstrasser, Proc. Natl. Acad. Sci. U.S.A. 96, 2036 (1999).
http://dx.doi.org/10.1073/pnas.96.5.2036
15.
15.To check the validity of the harmonic approximation in estimating the first-order correction, we have also calculated the first-order correction when using anharmonic instead of harmonic vibrational wave functions. Using a Morse potential with parameters determined from the levels (and the expressions given in Ref. 38), we obtain . Hence, the more precise first-order correction is not exactly zero, but still only 1% of the second-order correction.
16.
16.L. D. Landau and E. M. Lifschitz, Quantum Mechanics, Non-relativistic Theory (Butterworths, London/Heinemann, Oxford, 1999).
17.
17.C. Perchard and J. P. Perchard, J. Raman Spectrosc. 3, 277 (1975).
http://dx.doi.org/10.1002/jrs.1250030216
18.
18.M. Musso, H. Torii, P. Ottaviani, A. Asenbaum, and M. G. Giorgini, J. Phys. Chem. A 106, 10152 (2002).
http://dx.doi.org/10.1021/jp021440a
19.
19.T. Uemura, S. Saito, Y. Mizutani, and K. Tominaga, Mol. Phys. 103, 37 (2005).
20.
20.C. H. Wang and J. McHale, J. Chem. Phys. 72, 4039 (1980).
http://dx.doi.org/10.1063/1.439683
21.
21.D. E. Logan, Chem. Phys. 103, 215 (1986).
http://dx.doi.org/10.1016/0301-0104(86)80022-2
22.
22.H. Torii, J. Phys. Chem. A 103, 2843 (1999).
http://dx.doi.org/10.1021/jp9842650
23.
23.M. Pagliai, G. Cardini, R. Righini, and V. Schettino, J. Chem. Phys. 119, 6655 (2003).
http://dx.doi.org/10.1063/1.1605093
24.
24.J.-W. Handgraaf, E. J. Meijer, and M.-P. Gaigeot, J. Chem. Phys. 121, 10111 (2004).
http://dx.doi.org/10.1063/1.1809595
25.
25.A. Moran and S. Mukamel, Proc. Natl. Acad. Sci. U.S.A. 101, 506 (2004).
http://dx.doi.org/10.1073/pnas.2533089100
26.
26.J. E. Bertie and S. L. Zhang, J. Mol. Struct. 413, 333 (1997).
http://dx.doi.org/10.1016/S0022-2860(97)00152-X
27.
27.A. H. Narten and A. Habenschuss, J. Chem. Phys. 80, 3387 (1984).
http://dx.doi.org/10.1063/1.447093
28.
28.The uncertainty in this value is an underestimate, since there exists a distribution of distances and transition-dipole moments , and the calculated may differ from the ensemble average .
29.
29.S. Mukamel, Annu. Rev. Phys. Chem. 51, 691 (2000).
http://dx.doi.org/10.1146/annurev.physchem.51.1.691
30.
30.D. M. Jonas, Annu. Rev. Phys. Chem. 54, 425 (2003).
http://dx.doi.org/10.1146/annurev.physchem.54.011002.103907
31.
31.M. Cho, Bull. Korean Chem. Soc. 27, 1940 (2007).
32.
32.O. Golonzka, M. Khalil, N. Demirdöven, and A. Tokmakoff, Phys. Rev. Lett. 86, 2154 (2001).
http://dx.doi.org/10.1103/PhysRevLett.86.2154
33.
33.A. T. Krummel and M. T. Zanni, J. Phys. Chem. B 110, 13991 (2006).
http://dx.doi.org/10.1021/jp062597w
34.
34.C. P. Lawrence and J. L. Skinner, J. Chem. Phys. 118, 264 (2003).
http://dx.doi.org/10.1063/1.1525802
35.
35.C. J. Fecko, J. D. Eaves, J. J. Loparo, A. Tokmakoff, and P. L. Geissler, Science 301, 1698 (2003).
http://dx.doi.org/10.1126/science.1087251
36.
36.W. Feller, An Introduction to Probability Theory and Its Applications (Wiley, New York, 1968), Vol. I.
37.
37.T. Hayashi and S. Mukamel, J. Chem. Phys. 125, 194510 (2006).
http://dx.doi.org/10.1063/1.2348865
38.
38.R. H. Tipping and J. F. Ogilvie, J. Chem. Phys. 79, 2537 (1983).
http://dx.doi.org/10.1063/1.446165
http://aip.metastore.ingenta.com/content/aip/journal/jcp/127/15/10.1063/1.2779033
Loading
View: Figures

Figures

Image of FIG. 1.

Click to view

FIG. 1.

(a) Absorption spectra of mixtures with increasing molar fractions ( absorption subtracted). (b) The same spectra, scaled to the OH-stretch overtone intensity at . The overtone intensity is scaled at instead of at the band maximum of , since at the latter frequency the simultaneous absorption also contributes to the absorption (see upper panel).

Image of FIG. 2.

Click to view

FIG. 2.

Solid curve: simultaneous absorption band, obtained by subtracting the absorption with from that with . Dashed curve: absorption spectrum, multiplied horizontally by a factor of 2. The simultaneous absorption occurs at a frequency higher than twice the fundamental frequency.

Image of FIG. 3.

Click to view

FIG. 3.

log-log plot of the intensities of the overtone and simultaneous absorption per centimeter vs . The overtone absorption intensity is determined at . The simultaneous absorption is determined at , after subtracting the overtone absorption at this frequency. The latter is determined from the spectrum observed for , in which the simultaneous absorption is negligible. Also shown are lines with slopes of 1 and 2, corresponding to linear and quadratic concentration dependences, respectively.

Image of FIG. 4.

Click to view

FIG. 4.

Energy-level diagram (not to scale) for the OH-stretch two-exciton states. On the left the energy levels in absence of interaction between the two OH groups (isolated OH groups), on the right the energy levels when the molecules are neighbors.

Image of FIG. 5.

Click to view

FIG. 5.

(Color online) Solid curve: simultaneous absorption band. Dashed curve: fundamental absorption band. Both bands have been centered at the origin. The small residual absorption at the low-frequency side of the fundamental band is caused by the wing of the CD-stretch absorption band at . Dotted curves: fundamental absorption band, horizontally multiplied by a factor of and by a factor 2. These two curves are the simultaneous absorption bands expected if the two coupled OH-oscillators are completely uncorrelated , and completely correlated , respectively. The experimental simultaneous absorption band is between the and curves, indicating that the OH-frequencies are partially correlated.

Loading

Article metrics loading...

/content/aip/journal/jcp/127/15/10.1063/1.2779033
2007-10-19
2014-04-19

Abstract

We have investigated the simultaneous absorption of near-infrared photons by pairs of neighboring molecules in liquid methanol. Simultaneous absorption by two OH-stretching modes is found to occur at an energy higher than the sum of the two absorbing modes. This frequency shift arises from interaction between the modes, and its value has been used to determine the average coupling between neighboring methanol molecules. We find a rms coupling strength of , larger than can be explained from a transition-dipole coupling mechanism, suggesting that hydrogen-bond mediated interactions also contribute to the coupling. The most important aspect of simultaneous vibrational absorption is that it allows for a quantitative investigation of hydrogen-bond cooperativity. We derive the extent to which the hydrogen-bond strengths of neighboring molecules are correlated by comparing the line shape of the absorption band caused by simultaneous absorption with that of the fundamental transition. Surprisingly, neighboring hydrogen bonds in methanol are found to be strongly correlated, and from the data we obtain an estimate for the hydrogen-bond correlation coefficient of .

Loading

Full text loading...

/deliver/fulltext/aip/journal/jcp/127/15/1.2779033.html;jsessionid=9ei5qmg8rkmf6.x-aip-live-02?itemId=/content/aip/journal/jcp/127/15/10.1063/1.2779033&mimeType=html&fmt=ahah&containerItemId=content/aip/journal/jcp
true
true
This is a required field
Please enter a valid email address
752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Simultaneous photon absorption as a probe of molecular interaction and hydrogen-bond cooperativity in liquids
http://aip.metastore.ingenta.com/content/aip/journal/jcp/127/15/10.1063/1.2779033
10.1063/1.2779033
SEARCH_EXPAND_ITEM