skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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:
 [1];  [2];  [1];  [3];  [2];  [2];  [4]
  1. Univ. of Colorado, Boulder, CO (United States). JILA
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  3. National Inst. of Standards and Technology (NIST), Boulder, CO (United States)
  4. Univ. of Colorado, Boulder, CO (United States). JILA and Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
National Renewable Energy Lab. (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. doi: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. doi: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 = {2016},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Save / Share: