Femtosecond Measurements Of Size-Dependent Spin Crossover In FeII(pyz)Pt(CN)4 Nanocrystals
Abstract
We report a femtosecond time-resolved spectroscopic study of size-dependent dynamics in nanocrystals (NCs) of Fe(pyz)Pt(CN)4. We observe that smaller NCs (123 or 78 nm cross section and < 25 nm thickness) exhibit signatures of spin crossover (SCO) with time constants of ~ 5-10 ps whereas larger NCs with 375 nm cross section and 43 nm thickness exhibit a weaker SCO signature accompanied by strong spectral shifting on a ~20 ps time scale. For the small NCs, the fast dynamics appear to result from thermal promotion of residual low-spin states to high-spin states following nonradiative decay, and the size dependence is postulated to arise from differing high-spin vs low-spin fractions in domains residing in strained surface regions. The SCO is less efficient in larger NCs owing to their larger size and hence lower residual LS/HS fractions. Our results suggest that size-dependent dynamics can be controlled by tuning surface energy in NCs with dimensions below ~25 nm for use in energy harvesting, spin switching, and other applications.
- Authors:
-
- Univ. of Colorado, Boulder, CO (United States). JILA
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- National Inst. of Standards and Technology (NIST), Boulder, CO (United States)
- Univ. of Colorado, Boulder, CO (United States). JILA and Dept. of Chemistry and Biochemistry
- Publication Date:
- Research Org.:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1239050
- Report Number(s):
- NREL/JA-5900-64263
Journal ID: ISSN 1948-7185
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 1; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 14 SOLAR ENERGY; 77 NANOSCIENCE AND NANOTECHNOLOGY; femtosecond; spin-crossover; nanocrystals; time-resolved spectroscopy; high spin; low spin; transient absorption
Citation Formats
Sagar, D. M., Baddour, Frederick G., Konold, Patrick, Ullom, Joel, Ruddy, Daniel A., Johnson, Justin C., and Jimenez, Ralph. Femtosecond Measurements Of Size-Dependent Spin Crossover In FeII(pyz)Pt(CN)4 Nanocrystals. United States: N. p., 2016.
Web. doi:10.1021/acs.jpclett.5b02435.
Sagar, D. M., Baddour, Frederick G., Konold, Patrick, Ullom, Joel, Ruddy, Daniel A., Johnson, Justin C., & Jimenez, Ralph. Femtosecond Measurements Of Size-Dependent Spin Crossover In FeII(pyz)Pt(CN)4 Nanocrystals. United States. https://doi.org/10.1021/acs.jpclett.5b02435
Sagar, D. M., Baddour, Frederick G., Konold, Patrick, Ullom, Joel, Ruddy, Daniel A., Johnson, Justin C., and Jimenez, Ralph. Thu .
"Femtosecond Measurements Of Size-Dependent Spin Crossover In FeII(pyz)Pt(CN)4 Nanocrystals". United States. https://doi.org/10.1021/acs.jpclett.5b02435. https://www.osti.gov/servlets/purl/1239050.
@article{osti_1239050,
title = {Femtosecond Measurements Of Size-Dependent Spin Crossover In FeII(pyz)Pt(CN)4 Nanocrystals},
author = {Sagar, D. M. and Baddour, Frederick G. and Konold, Patrick and Ullom, Joel and Ruddy, Daniel A. and Johnson, Justin C. and Jimenez, Ralph},
abstractNote = {We report a femtosecond time-resolved spectroscopic study of size-dependent dynamics in nanocrystals (NCs) of Fe(pyz)Pt(CN)4. We observe that smaller NCs (123 or 78 nm cross section and < 25 nm thickness) exhibit signatures of spin crossover (SCO) with time constants of ~ 5-10 ps whereas larger NCs with 375 nm cross section and 43 nm thickness exhibit a weaker SCO signature accompanied by strong spectral shifting on a ~20 ps time scale. For the small NCs, the fast dynamics appear to result from thermal promotion of residual low-spin states to high-spin states following nonradiative decay, and the size dependence is postulated to arise from differing high-spin vs low-spin fractions in domains residing in strained surface regions. The SCO is less efficient in larger NCs owing to their larger size and hence lower residual LS/HS fractions. Our results suggest that size-dependent dynamics can be controlled by tuning surface energy in NCs with dimensions below ~25 nm for use in energy harvesting, spin switching, and other applications.},
doi = {10.1021/acs.jpclett.5b02435},
journal = {Journal of Physical Chemistry Letters},
number = 1,
volume = 7,
place = {United States},
year = {Thu Jan 07 00:00:00 EST 2016},
month = {Thu Jan 07 00:00:00 EST 2016}
}
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Works referencing / citing this record:
Finite Size Effects on the Switching Dynamics of Spin‐Crossover Thin Films Photoexcited by a Femtosecond Laser Pulse
journal, April 2019
- Ridier, Karl; Bas, Alin‐Ciprian; Shalabaeva, Victoria
- Advanced Materials, Vol. 31, Issue 25