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  • Editor: Alan E. Willner
  • Vol. 38, Iss. 18 — Sep. 15, 2013
  • pp: 3596–3599
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Waveguide-enhanced 2D-IR spectroscopy in the gas phase

Gregory M. Greetham, Ian P. Clark, Damien Weidmann, Michael N. R. Ashfold, Andrew J. Orr-Ewing, and Michael Towrie  »View Author Affiliations


Optics Letters, Vol. 38, Issue 18, pp. 3596-3599 (2013)
http://dx.doi.org/10.1364/OL.38.003596


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Abstract

A method for obtaining high-quality 2D-IR spectra of gas-phase samples is presented. Time-resolved IR absorption spectroscopy techniques, such as 2D-IR spectroscopy, often require that beams are focused into the sample. This limits the exploitable overlapped path length through samples to a few millimeters. To circumvent this limitation, 2D-IR experiments have been performed within a hollow waveguide. This has enabled acquisition of 2D-IR spectra of low-concentration gas-phase samples, with more than an order of magnitude signal enhancement compared with the equivalent experiment in free space. The technique is demonstrated by application to the 2D-IR spectroscopy of iron pentacarbonyl.

© 2013 Optical Society of America

Ultrafast time-resolved IR absorption spectroscopy is a useful approach for studying dynamic structural changes. In particular, over the last 15 years, 2D-IR spectroscopy [1

1. P. Hamm, M. H. Lim, and R. M. Hochstrasser, J. Phys. Chem. B 102, 6123 (1998). [CrossRef]

,2

2. N. T. Hunt, Chem. Soc. Rev. 38, 1837 (2009). [CrossRef]

] has been successfully applied to studies of a range of structural dynamics [3

3. M. L. Cowan, B. D. Bruner, N. Huse, J. R. Dwyer, B. Chugh, E. T. J. Nibbering, T. Elsaesser, and R. J. D. Miller, Nature 434, 199 (2005). [CrossRef]

,4

4. C. R. Baiz, P. L. McRobbie, J. M. Anna, E. Geva, and K. J. Kubarych, Acc. Chem. Res. 42, 1395 (2009). [CrossRef]

] and energy transfer processes [5

5. V. Botan, E. H. G. Backus, R. Pfister, A. Moretto, M. Crisma, C. Toniolo, P. H. Nguyen, G. Stock, and P. Hamm, Proc. Natl. Acad. Sci. U.S.A. 104, 12749 (2007). [CrossRef]

,6

6. V. M. Kasyanenko, P. Keiffer, and I. V. Rubtsov, J. Chem. Phys. 136, 144503 (2012). [CrossRef]

]. A wide range of approaches involve pulsed IR excitation and IR probing of samples providing detailed dynamical information about vibrational coupling and exchange in molecules.

In the condensed-phase, 2D-IR spectroscopy has become a mature field, even extending its application to large biological systems [2

2. N. T. Hunt, Chem. Soc. Rev. 38, 1837 (2009). [CrossRef]

]. However, the use of the technique to study gas-phase samples is still limited. When studying a chemical reaction, the role of the environment cannot be ignored. In the case of condensed-phase 2D-IR experiments, one often considers whether energy transfer or ligand exchange processes are truly intramolecular or solvent-mediated. Solution-phase experiments are usually performed under a variety of conditions (e.g., in different solvents) to resolve such ambiguity. The possibility to perform such experiments in the gas phase offers an opportunity to remove solvent effects altogether.

To increase the effective path length of a gas-phase 2D-IR measurement to >90mm, we performed experiments inside a square hollow IR waveguide [12

12. D. Weidmann, B. J. Perrett, N. A. Macleod, and R. M. Jenkins, Opt. Express 19, 9074 (2011). [CrossRef]

], made from polycrystalline Macor ceramic. Signal intensity is enhanced by more than an order of magnitude as compared with unguided measurements, despite some laser intensity losses incurred by transport through the waveguide.

2D-IR spectra of Fe(CO)5 vapor were taken using a double-resonance approach [2

2. N. T. Hunt, Chem. Soc. Rev. 38, 1837 (2009). [CrossRef]

], with a narrowband (10cm1, 2 ps duration) pump pulse and a broadband (300cm1, 50 fs duration) probe pulse. The IR pulses were generated from a 10 kHz repetition rate, dual picosecond/femtosecond titanium sapphire amplified laser described previously [14

14. G. M. Greetham, P. Burgos, Q. Cao, I. P. Clark, P. S. Codd, R. C. Farrow, M. W. George, M. Kogimtzis, P. Matousek, A. W. Parker, M. R. Pollard, D. A. Robinson, Z. J. Xin, and M. Towrie, Appl. Spectrosc. 64, 1311 (2010). [CrossRef]

]. Synchronized picosecond and femtosecond 800 nm outputs from the titanium sapphire laser pumped two optical parametric amplifiers (OPAs), with IR generation achieved through signal and idler difference frequency generation. Pump and probe pulses were combined at a 50% beam splitter, propagated collinearly, and focused to spot sizes of 100μm diameter in the gas cell containing the sample, as shown in Fig. 1. After propagating through the sample, the expanding IR beams were recollimated and directed to an IR spectrograph. In experiments where the waveguide was omitted from the gas cell, the collimating lens was adjusted accordingly. The two beams had orthogonal polarizations (pump vertical and probe horizontal), so that the pump beam could be removed from the collinear probe beam after the sample by positioning a polarizer just before the spectrograph. It should be noted that the use of orthogonal polarization is a limitation in these experiments, introducing anisotropy effects into the measurement (usually avoided through measurement at magic angle [13

13. J. F. Cahoon, K. R. Sawyer, J. P. Schlegel, and C. B. Harris, Science 319, 1820 (2008). [CrossRef]

]). Future studies aim to address the impact of this constraint on the present demonstration and methods to circumvent the limitation. Pump pulse energies were 500nJ, and the relative timing of the pump and probe pulses was computer-controlled by an optical delay line. 2D-IR spectra were accumulated by computer-controlled scanning of the pump OPA wavelength and recording normalized pump on–pump off difference spectra at each position.

Fig. 1. Experimental layout. The waveguide is placed inside a sealed cell, with CaF2 windows, containing the sample. Pump and probe beams are combined at a beam splitter (B) and focused (f1) onto the waveguide entrance. After passing through the waveguide, the beams are collimated (f2), the pump beam removed by a polarizer (P), and the probe beam sent to a spectrograph.

Fe(CO)5 vapor was prepared in the 100 mm long nonevacuable gas cell (with CaF2 windows on each end) by placing 1ml volume of a 2 mM solution of Fe(CO)5 in n-heptane. The vapor diffused throughout the cell within minutes, creating an optical density (OD) of 0.4 at the 5 μm absorption maximum of gas-phase Fe(CO)5. The sample was diluted in heptane to reduce the vapor pressure, as a room temperature sample of pure Fe(CO)5 has an OD >4 at this wavelength. The heptane vapor has no significant absorption in this spectral region. The waveguide was placed inside the gas cell and aligned onto the beam.

The waveguides used in this study had lengths of 84 or 97 mm. Results obtained using 300 μm wide waveguides of both lengths were compared, and <10% difference in signal intensity observed. This probably reflects the inefficient transmission through the waveguides (see below), with the major pump contribution to the signal coming from the early part of the waveguide.

Important considerations when taking measurements of samples inside the waveguide are: (i) the IR beams are propagated with minimum loss, (ii) time resolution is not lost due to excitation of multiple waveguide modes, (iii) polarization is preserved in the waveguide and that there is no perturbation of the spectrum or dynamics due to (iv) measurement in the waveguide compared to free gas or (v) due to surface effects.
  • (i) Previous tests on a 1 mm wide hollow waveguide with 10μm wavelength quantum cascade lasers showed that, with correct mode matching, >98% transmission is achievable [15

    15. R. M. Jenkins, R. W. J. Devereux, and A. F. Blockley, J. Mod. Opt. 45, 1613 (1998).

    ], close to the expected theoretical transmission. The transmission scales with the guide width. At 5 μm, the maximum theoretical transmission through an 84 mm long hollow waveguide would be 96%, 88%, and 56% for a 300, 200, and 120 μm guide width, respectively [15

    15. R. M. Jenkins, R. W. J. Devereux, and A. F. Blockley, J. Mod. Opt. 45, 1613 (1998).

    ]. With the ultrafast lasers used here at 5μm wavelength, >25% was achieved. This additional loss suggests that high-order hybrid modes are excited within the waveguide due to non-TEM00 Gaussian beams, imperfect angular and axial coupling conditions, and increased scattering of the waveguide surfaces. Indeed, even though the arithmetic average surface roughness of the waveguide wall is 0.5μm, the maximum peak to valley roughness can be as high as 5μm. For the present demonstration, this loss of power through the waveguide reduces the observed signal strength as the compromised pump power reduces the excitation efficiency. However, the >10-fold increase in signal intensity demonstrated below (Fig. 2) demonstrates the principle of improvement in 2D-IR spectra, despite these transmission losses. With improved waveguide surface quality and spatial mode matching of the ultrafast laser to the waveguide, one may expect at least a further twofold improvement over the present results.
  • (ii) A time-resolved IR absorption cross correlation of the IR pulses with synchronized 50 fs, 400 nm pulses in germanium was made before and after passage through the waveguide (in air at atmospheric pressure). The difference in the cross-correlation rise time was <100fs. Any effect on pulse duration is therefore insignificant in these measurements, as a 2 ps long pump pulse is used.
  • (iii) Polarizers before and after the waveguide confirmed the polarization to be preserved after passing through the waveguide at a level of >3001.
  • (iv) The flow of fresh sample through the waveguide is restricted compared with the open gas but we are not damaging the molecule by dissociation or generating long-lived excited states in these 2D-IR experiments. Repumping the same part of the sample at the 5 kHz repetition rate of the pump pulses is thus acceptable.
  • (v) A potential perturbation in the measurements could come from surface-associated or condensed-phase sample in the waveguide. Significant condensation could occur if the waveguide temperature were lower than the sample temperature, or if there were high sample vapor pressure. In these experiments, all apparatus was maintained at 293 K and the vapor pressure was very low [cf. a pure Fe(CO)5 sample]. Calculated intensity distributions [9

    9. V. Krylov, A. Kushnarenko, E. Miloglyadov, M. Quack, and G. Seyfang, Proc. SPIE 6460, 64601D (2007). [CrossRef]

    ,12

    12. D. Weidmann, B. J. Perrett, N. A. Macleod, and R. M. Jenkins, Opt. Express 19, 9074 (2011). [CrossRef]

    ] predict that the amplitude of the laser beam at the edges of the waveguide is necessarily low. To confirm these assumptions, free gas 2D-IR spectra and kinetics were measured for Fe(CO)5 vapor and compared with the waveguide-enhanced 2D-IR spectra and kinetics. No discernible differences were observed in the data with or without the waveguide, except for a significant improvement in the signal to noise when the waveguide is used.

Fig. 2. Normalized IR pump–IR probe difference spectra, illustrating the signal increase with decreasing waveguide width (shown in the legend, with None referring to the measurement with no waveguide present). All spectra were taken with 2 ps delay between pump and probe. A, pump at 2013cm1; B, pump at 2034cm1.

Figure 2 shows the enhancement in IR pump–IR probe difference spectra as the waveguide width is reduced. The signal intensity increases by a factor of 15 between the free gas and the smallest (200 μm wide) waveguide. A simple model of signal accumulation in the empty or waveguided cell takes into account the focusing and waveguided pump beam cross-section area as it propagates through the cell and pump intensity losses due to sample absorbance (and in the waveguided case, losses from transmission efficiency). From this model, signal gain is expected to be 12-fold in the 200 μm wide waveguide, close to the value of 15-fold measured experimentally. The Fourier transform infrared (FTIR) spectrum of Fe(CO)5 vapor (Fig. 3A) in the 2000cm1 region shows two main absorptions associated with the e and a2 modes (with wavenumbers of 2013 and 2034cm1, effectively equatorial and axial CO stretch modes, respectively). When pumping at 2013cm1 (Fig. 2A), a negative “bleach” signal appears at this wavenumber, associated with loss of absorbance and increase of stimulated emission on the v=10 transition, as v=0 population is reduced and v=1 population increased. The positive “transient” signal shifted by 15cm1 to lower wavenumber, is associated with the corresponding increase in the v=21 absorption, as the v=1 population is increased. The 15cm1 shift reflects an harmonicity with increasing vibrational excitation. Some additional structure is evident, attributable to the partially resolved rotational band envelope and, potentially, to ladder climbing as v=1 population can be further excited to v=2. Figure 2B shows the equivalent difference spectrum when pumping the 2034cm1 band. Some weak excitation of the neighboring band is evident in Figs. 2A and 2B, due to the 10cm1 bandwidth of the pump laser.

Fig. 3. A, FTIR spectrum of Fe(CO)5 vapor. Waveguide-enhanced 2D-IR spectra of Fe(CO)5 vapor with B, 2 ps time delay between pump and probe and C, 240 ps time delay between pump and probe. B and C, 2D-IR spectra color gradients are given as OD change values in the legends.

The waveguide-enhanced 2D-IR spectroscopy technique reported here is shown to enable >10-fold enhanced transient signal intensities as a result of the extended path length of IR pump–IR probe overlap—a benefit that is not experienced under normal gas-phase experimental conditions due to focusing limitations of mid-IR laser beams. The technique has been applied to gas-phase studies of ligand exchange dynamics in Fe(CO)5, demonstrating substantial improvement in SNR. From this first demonstration, further SNR improvement is expected by improving the pump probe field coupling into the waveguide.

This method can be further applied to obtain high-quality 2D-IR spectra in the gas phase, with potential to improve data quality in low concentration gas-phase samples (e.g., gas phase dimers [8

8. S. T. Shipman, P. C. Douglass, H. S. Yoo, C. E. Hinkle, E. L. Mierzejewski, and B. H. Pate, Phys. Chem. Chem. Phys. 9, 4572 (2007). [CrossRef]

]), as well as providing scope for a range of structural dynamics and energy transfer studies.

The authors are grateful for access to the STFC ULTRA laser facility. The STFC Centre for Instrumentation in Advanced Optics is acknowledged for the waveguide developments. MNRA and AJOE are grateful to EPSRC for funding via Programme Grant EP/G00224X, and AJOE thanks the ERC for support through Advanced Grant 290966 CAPRI.

References

1.

P. Hamm, M. H. Lim, and R. M. Hochstrasser, J. Phys. Chem. B 102, 6123 (1998). [CrossRef]

2.

N. T. Hunt, Chem. Soc. Rev. 38, 1837 (2009). [CrossRef]

3.

M. L. Cowan, B. D. Bruner, N. Huse, J. R. Dwyer, B. Chugh, E. T. J. Nibbering, T. Elsaesser, and R. J. D. Miller, Nature 434, 199 (2005). [CrossRef]

4.

C. R. Baiz, P. L. McRobbie, J. M. Anna, E. Geva, and K. J. Kubarych, Acc. Chem. Res. 42, 1395 (2009). [CrossRef]

5.

V. Botan, E. H. G. Backus, R. Pfister, A. Moretto, M. Crisma, C. Toniolo, P. H. Nguyen, G. Stock, and P. Hamm, Proc. Natl. Acad. Sci. U.S.A. 104, 12749 (2007). [CrossRef]

6.

V. M. Kasyanenko, P. Keiffer, and I. V. Rubtsov, J. Chem. Phys. 136, 144503 (2012). [CrossRef]

7.

C. Stromberg, D. J. Myers, and M. D. Fayer, J. Chem. Phys. 116, 3540 (2002). [CrossRef]

8.

S. T. Shipman, P. C. Douglass, H. S. Yoo, C. E. Hinkle, E. L. Mierzejewski, and B. H. Pate, Phys. Chem. Chem. Phys. 9, 4572 (2007). [CrossRef]

9.

V. Krylov, A. Kushnarenko, E. Miloglyadov, M. Quack, and G. Seyfang, Proc. SPIE 6460, 64601D (2007). [CrossRef]

10.

F. Benabid, J. C. Knight, G. Antonopoulos, and P. St. J. Russell, Science 298, 399 (2002). [CrossRef]

11.

F. Eftekhari, J. Irizar, L. Hulbert, and A. S. Helmy, J. Appl. Phys. 109, 113104 (2011). [CrossRef]

12.

D. Weidmann, B. J. Perrett, N. A. Macleod, and R. M. Jenkins, Opt. Express 19, 9074 (2011). [CrossRef]

13.

J. F. Cahoon, K. R. Sawyer, J. P. Schlegel, and C. B. Harris, Science 319, 1820 (2008). [CrossRef]

14.

G. M. Greetham, P. Burgos, Q. Cao, I. P. Clark, P. S. Codd, R. C. Farrow, M. W. George, M. Kogimtzis, P. Matousek, A. W. Parker, M. R. Pollard, D. A. Robinson, Z. J. Xin, and M. Towrie, Appl. Spectrosc. 64, 1311 (2010). [CrossRef]

15.

R. M. Jenkins, R. W. J. Devereux, and A. F. Blockley, J. Mod. Opt. 45, 1613 (1998).

OCIS Codes
(140.3490) Lasers and laser optics : Lasers, distributed-feedback
(230.7370) Optical devices : Waveguides
(300.6340) Spectroscopy : Spectroscopy, infrared
(300.6500) Spectroscopy : Spectroscopy, time-resolved

ToC Category:
Spectroscopy

History
Original Manuscript: May 23, 2013
Revised Manuscript: June 28, 2013
Manuscript Accepted: August 16, 2013
Published: September 9, 2013

Citation
Gregory M. Greetham, Ian P. Clark, Damien Weidmann, Michael N. R. Ashfold, Andrew J. Orr-Ewing, and Michael Towrie, "Waveguide-enhanced 2D-IR spectroscopy in the gas phase," Opt. Lett. 38, 3596-3599 (2013)
http://www.opticsinfobase.org/ol/abstract.cfm?URI=ol-38-18-3596


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References

  1. P. Hamm, M. H. Lim, and R. M. Hochstrasser, J. Phys. Chem. B 102, 6123 (1998). [CrossRef]
  2. N. T. Hunt, Chem. Soc. Rev. 38, 1837 (2009). [CrossRef]
  3. M. L. Cowan, B. D. Bruner, N. Huse, J. R. Dwyer, B. Chugh, E. T. J. Nibbering, T. Elsaesser, and R. J. D. Miller, Nature 434, 199 (2005). [CrossRef]
  4. C. R. Baiz, P. L. McRobbie, J. M. Anna, E. Geva, and K. J. Kubarych, Acc. Chem. Res. 42, 1395 (2009). [CrossRef]
  5. V. Botan, E. H. G. Backus, R. Pfister, A. Moretto, M. Crisma, C. Toniolo, P. H. Nguyen, G. Stock, and P. Hamm, Proc. Natl. Acad. Sci. U.S.A. 104, 12749 (2007). [CrossRef]
  6. V. M. Kasyanenko, P. Keiffer, and I. V. Rubtsov, J. Chem. Phys. 136, 144503 (2012). [CrossRef]
  7. C. Stromberg, D. J. Myers, and M. D. Fayer, J. Chem. Phys. 116, 3540 (2002). [CrossRef]
  8. S. T. Shipman, P. C. Douglass, H. S. Yoo, C. E. Hinkle, E. L. Mierzejewski, and B. H. Pate, Phys. Chem. Chem. Phys. 9, 4572 (2007). [CrossRef]
  9. V. Krylov, A. Kushnarenko, E. Miloglyadov, M. Quack, and G. Seyfang, Proc. SPIE 6460, 64601D (2007). [CrossRef]
  10. F. Benabid, J. C. Knight, G. Antonopoulos, and P. St. J. Russell, Science 298, 399 (2002). [CrossRef]
  11. F. Eftekhari, J. Irizar, L. Hulbert, and A. S. Helmy, J. Appl. Phys. 109, 113104 (2011). [CrossRef]
  12. D. Weidmann, B. J. Perrett, N. A. Macleod, and R. M. Jenkins, Opt. Express 19, 9074 (2011). [CrossRef]
  13. J. F. Cahoon, K. R. Sawyer, J. P. Schlegel, and C. B. Harris, Science 319, 1820 (2008). [CrossRef]
  14. G. M. Greetham, P. Burgos, Q. Cao, I. P. Clark, P. S. Codd, R. C. Farrow, M. W. George, M. Kogimtzis, P. Matousek, A. W. Parker, M. R. Pollard, D. A. Robinson, Z. J. Xin, and M. Towrie, Appl. Spectrosc. 64, 1311 (2010). [CrossRef]
  15. R. M. Jenkins, R. W. J. Devereux, and A. F. Blockley, J. Mod. Opt. 45, 1613 (1998).

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