Ultrafast Vibrational Dynamics of NO and CO Adsorbed on an Iridium Surface

Lane, Ian M.; Liu, Zhi-Pan; King, David A.; Arnolds, Heike

doi:10.1021/jp071831v

Cited by 17 publications

(11 citation statements)

References 59 publications

(104 reference statements)

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“…For NO on Ir (111) the frustrated rotation is found to respond to hot electrons at a time scale of 700 fs. 116 In agreement with our calculations, Abe and Yamashita 124 have estimated the NO on Pt(111) IS mode lifetime to be roughly 4 times shorter than the CO on Cu(111) lifetime, which when applied to our case would amount to 1.4 ps. We find 1.32 ps.…”

Section: Vibrational Relaxation Of Diatomic Molecules On Metal Sursupporting

confidence: 90%

“…In such cases nonadiabatic energy loss can be measured by pump-probe spectroscopy 4,77 and indirectly by using substrate laser-heating. 115,116 One of the most studied systems is the internal stretch (IS) motion of CO adsorbed on Cu(100). 4,5,67,115,117 The vibrational frequencies of CO have been measured to be 2078 cm −1 (257.8 meV) for the internal stretch (IS) mode, 114 345 cm −1 (42.8 meV) 114 for the surface-adsorbate stretch (SA), 288 cm −1 (35.3 meV) 114 for the frustrated rotation (FR) and 32 cm −1 (4 meV) 118 the frustrated translation (FT) (see also Fig.…”

Section: Vibrational Relaxation Of Diatomic Molecules On Metal Surmentioning

confidence: 99%

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Ab initiotensorial electronic friction for molecules on metal surfaces: Nonadiabatic vibrational relaxation

et al. 2016

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Molecular adsorbates on metal surfaces exchange energy with substrate phonons and low-lying electron-hole pair excitations. In the limit of weak coupling, electron-hole pair excitations can be seen as exerting frictional forces on adsorbates that enhance energy transfer and facilitate vibrational relaxation or hot-electron mediated chemistry. We have recently reported on the relevance of tensorial properties of electronic friction [Phys. Rev. Lett. 116, 217601 (2016)] in dynamics at surfaces. Here we present the underlying implementation of tensorial electronic friction based on Kohn-Sham Density Functional Theory for condensed phase and cluster systems. Using local atomic-orbital basis sets, we calculate nonadiabatic coupling matrix elements and evaluate the full electronic friction tensor in the Markov limit. Our approach is numerically stable and robust as shown by a detailed convergence analysis. We furthermore benchmark the accuracy of our approach by calculation of vibrational relaxation rates and lifetimes for a number of diatomic molecules on metal surfaces. We find friction-induced mode-coupling between neighboring CO adsorbates on Cu(100) in a c(2x2) overlayer to be important to understand experimental findings.

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Section: Vibrational Relaxation Of Diatomic Molecules On Metal Sursupporting

confidence: 90%

Section: Vibrational Relaxation Of Diatomic Molecules On Metal Surmentioning

confidence: 99%

Ab initiotensorial electronic friction for molecules on metal surfaces: Nonadiabatic vibrational relaxation

et al. 2016

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“…Arnolds and coworkers proposed the electron transfer from the substrate to adsorbate contributes to the redshifts of stretching modes of NO and CO on Ir(111) under irradiation of pump pulses at 800 nm. 27,28 If this electron transfer effect is a dominating contribution to the observed redshifts of C-O stretching, the frequency shift will mimic the time evolution of electron temperature. Although the amount of redshift until 0.4 ps after the IR pulse correlates well with T e , the discrepancy between the two is evident after 0.4 ps: the amount of redshift decreases faster than T e .…”

Section: Resultsmentioning

confidence: 99%

Instantaneous vibrational frequencies of diffusing and desorbing adsorbates: CO/Pt(111)

Inoue

Watanabe

Matsumoto

2012

The Journal of Chemical Physics

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Electronic excitation of metal by intense laser pulses stimulates nuclear motions of adsorbates through nonadiabatic coupling, resulting in diffusion and desorption of adsorbates. These processes take place via precursor states: adsorbates whose vibrational modes with respect to substrate are highly excited. This paper reports the dynamics of precursor states of CO on Pt(111) probed by use of infrared-visible sum frequency generation with phase-sensitive detection, which allows us to obtain the second-order nonlinear susceptibility and thus the vibrational response function. Without pump pulses at 400 nm, the inverse Fourier transformation of the vibrational response function reveals a free induction decay of vibrational polarization of C-O stretching created by a short infrared pulse. The free induction decay is perturbed when an intense 400-nm pump pulse following the infrared pulse is irradiated, because diffusion and desorption of CO are induced by the pump pulse. The time evolution of instantaneous C-O stretching frequency retrieved from the perturbed free induction decay shows a redshift followed by a rapid reverse shift when the fluence of pump pulse is high enough to desorb CO. This indicates that the frustrated modes of CO is first substantially excited and then the parallel momentum of CO is converted to the normal one through mutual collisions, leading to substantial excitation of the external stretching mode of CO.

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“…In the original anharmonic coupling model [41], frequency changes observed following ultrafast excitation were generally expected to occur with the same sign as those observed by step-wise heating. For singly-coordinated CO, for which the most detailed data are available (e.g., [4,5,41,48]), the internal stretch frequency is generally seen to decrease as it couples anharmonically to the FT, which moves CO from an atop to a multiply coordinated site, which increases backdonation and reduces the frequency. Bridge site CO, however, is thought to anharmonically couple to different low frequency modes, which might reduce the overlap between 2π* and metal orbitals, thus causing a blue shift.…”

Section: Discussionmentioning

confidence: 99%

Ultrafast Vibrational Dynamics of CO Ligands on RuTPP/Cu(110) under Photodesorption Conditions

et al. 2019

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We have studied CO coordinated to ruthenium tetraphenylporphyrin (RuTPP)/Cu(110) and directly adsorbed to Cu(110), using femtosecond pump-sum frequency probe spectroscopy, to alter the degree of electron-vibration coupling between the metal substrate and CO. We observe the facile femtosecond laser-induced desorption of CO from RuTPP/Cu(110), but not from Cu(110). A change in the vibrational transients, in the first few picoseconds, from a red- to blue-shift of the C–O stretching vibration under photodesorption conditions, was also observed. This drastic change can be explained, if the cause of the C–O frequency redshift of Cu(110) is not the usually-assumed anharmonic coupling to low frequency vibrational modes, but a charge transfer from hot electrons to the CO 2π* state. This antibonding state shifts to higher energies on RuTPP, removing the C–O redshift and, instead, reveals a blueshift, predicted to arise from electron-mediated coupling between the coherently excited internal stretch and low frequency modes in the system.

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Ultrafast Vibrational Dynamics of NO and CO Adsorbed on an Iridium Surface

Cited by 17 publications

References 59 publications

Ab initiotensorial electronic friction for molecules on metal surfaces: Nonadiabatic vibrational relaxation

Ab initiotensorial electronic friction for molecules on metal surfaces: Nonadiabatic vibrational relaxation

Instantaneous vibrational frequencies of diffusing and desorbing adsorbates: CO/Pt(111)

Ultrafast Vibrational Dynamics of CO Ligands on RuTPP/Cu(110) under Photodesorption Conditions

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