This file FILENAME was updated on 2022-02-21 by Ziwei Yu ------------------- GENERAL INFORMATION ------------------- Recommended citation for the data: Yu, Ziwei; Frontiera, Renee. (2022). Supporting Data for "Intermolecular Forces Dictate Vibrational Energy Transfer in Plasmonic–Molecule Systems". Retrieved from the Data Repository for the University of Minnesota, https://doi.org/10.13020/gneg-dv46. Title of Dataset: Supporting Data for Intermolecular Forces Dictate Vibrational Energy Transfer in Plasmonic–Molecule Systems Author Information: Principal Investigator Contact Information Name:Renee Frontiera Institution: University of Minnesota Address: CHEMISTRY DEPARTMENT, 207 Pleasant St SE, Minneapolis, Minnesota 55455 Email:rrf@umn.edu ORCID:https://orcid.org/0000-0001-8218-7574 Associate or Co-investigator Contact information Name:Ziwei Yu Institution:University of Minnesota Address:CHEMISTRY DEPARTMENT, 207 Pleasant St SE, Minneapolis, Minnesota 55455 Email:yu000179@umn.edu Date of data collection (single date, range, approximate date): Ultrafast SERS spectra data was collected between 20210225 and 20210309. Geographic location of data collection (where was data collected?): University of Minnesota Information about funding sources that supported the collection of the data: This work was supported by Air Force Office of Scientific Research under AFOSR sward no. FA9550-15-1-0022. This work was supported partially by the MRSEC Program of the National Science Foundation under award no. DMR-2011401. -------------------------- SHARING/ACCESS INFORMATION -------------------------- 1. Licenses/restrictions placed on the data: Depositor did not specify a license. Material may be reused with appropriate attribution. 2. Links to publications that cite or use the data: https://doi.org/10.1021/acsnano.1c08431 3. Links to other publicly accessible locations of the data: 4. Links/relationships to ancillary data sets: 5. Was data derived from another source? --------------------- DATA & FILE OVERVIEW --------------------- Under each top-level file or folder, add description of the data, file formats, software required to open, and any other information (e.g., conditions, filenaming, etc.) to help understand, explain, and navigate the files. 1. File List A. Filename: SERS Spectra Fitting Short description: File Folder containing all the raw spectra and peak fitting code and procedure for data used in the paper. (software required to open: Igor) In the folder, multiple Igor files (.pxp) are present with the name of each Igor file containing information about the sample associated with the data set. (Example: 0223#16CTP_L1_AS1 : 0223-->date substrate was made; #16-->substrate code; CTP-->analyte molecule; L1-->location 1 on this substrate; AS1-->first set of anti-Stokes scan.) B. Filename: Kinetic Trace Fitting Short description: Igor file containing the population ratio kinetic traces from all scans, and the fitting code and procedure for fitting the kinetic traces.(software required to open: Igor) C. Filename:Data Collection Summary Short description: Excel spreadsheet documenting the date that each data set (in the 'SERS Spectra Fitting' Folder) was taken and the simplified names of each data set used for kinetic trace fitting. A summary of the kinetic trace fitting results. D. Filename:UV spectra Short description: Igor file containing the extinction spectra of the substrates used in the experiments. E. Filename:SEM File folder with the SEM images of the substrates used in the experiments. 2. Relationship between files: 'SERS Spectra Fitting' Folder has the raw data and the data analysis of the SERS spectra that forms the data in the 'Kinetic Trace Fitting' file. The 'Data Collection Summary' file has the documentation of the name conversion of the data set name used in 'SERS Spectra Fitting' and 'Trace Fitting'. The 'Data Collection Summary' file also recorded the output from the kinetic trace fitting in the 'Kinetic Trace Fitting' file. 3. Additional related data collected that was not included in the current data package: None 4. Are there multiple versions of the dataset? N -------------------------- METHODOLOGICAL INFORMATION -------------------------- 1. Description of methods used for collection/generation of data [Copy the methods section from the paper (if that covers it), write up more detailed methods if necessary]: We took the ultrafast SERS measurements with a home-written Labview program. Each Stokes scan consists of Stokes spectra taken at different time delays, as does the anti-Stokes scan. Each complete set of transient data has one Stokes scan and two anti-Stokes scans, with the Stokes scan taken between the two anti-Stokes scans. We averaged the anti-Stokes spectra of corresponding time delays from the two scans together to eliminate the bias introduced by sample degradation over the period of measurement. At each timepoint, we used a pump-only spectrum of the same acquisition time to subtract out the pump-induced broad background. The acquisition time is 30s for anti-Stokes spectra and 20s for Stokes spectra. We normalized the intensity of each spectrum with the acquisition time. For each sample, we took the measurement at three different locations. At each location, we first illuminated the sample for 30 min with a 20mW picosecond laser, and then 60 min with both a 20mW picosecond and a 20mW femtosecond laser overlapped. This step is to stabilize the substrate as shown in Figure S3a and minimize the discrepancy introduced by sample degradation during the measurement. After the illumination, we took the first set of transient data. Then we illuminated the substrate for another 60 min with the 20mW picosecond and the 20mW femtosecond laser before taking another set of transient data at the same location. We controlled the illumination time to be the same for all samples. 2. Methods for processing the data: We fitted each Stokes and anti-Stokes individually with Gaussian peak(s) with a linear baseline. For CTP and NBT, two peaks are needed to best fit the Stokes peaks, however, the corresponding anti-Stokes cannot be deconvoluted into two peaks because of the lower signal-tonoise ratio. Therefore, we added the peak area of the two fitted Stokes peaks together for following analysis. For MTP, PTP and BT, we used one Gaussian peak to fit both anti-Stokes and Stokes peaks. To determine the detector efficiency, we obtained the specification sheets for the gratings (600 gr/mm blazed at 750 nm, Richardson Gratings) and the InGaAs array (Pylon-IR 1.7, Princeton Instruments). We then calculated the detector efficiency by multiplying the grating and the InGaAs array efficiency at the anti-Stokes and Stokes scattering wavelength. To obtain the normalized anti-Stokes and Stokes scattering intensities, we divided the peak amplitude obtained from the peak fitting by the detector efficiency and extinction factor at corresponding wavelength. Then we calculated the excited/ground state population ratio with the normalized anti-Stokes and Stokes scattering intensities thorugh Boltzmann analysis. We propagated the errors from peak fitting to get the error for each population ratio value. We plotted the calculated population ratio as a function of delay time to get the transient kinetic traces, which are then fitted with an exponential decay convoluted with the instrument response. For each aromatic thiol, we obtained six kinetic traces at three different sample spots. We define the baseline population ratio as the baseline, the population ratio increase at time zero as transient increase, and the time constant of the exponential decay as lifetime. The we ran t tests for baseline, transient increase and lifetime with every two aromatic thiols to determine the significance of difference. 3. Instrument- or software-specific information needed to interpret the data: Igor Pro 7.00 is used for the data analysis. 4. Standards and calibration information, if appropriate: 5. Environmental/experimental conditions: All experiments were conducted at room temperature under a temperature/humidity controlled lab condition. 6. Describe any quality-assurance procedures performed on the data: Multiple datasets were taken for each molecule, which includes dataset at different sample locations and datasets taken repeatedly on the same location to verify to reproducibility of the results. Error analysis were taken to indicate the interval of confidence for the results. 7. People involved with sample collection, processing, analysis and/or submission: List people and their role. Ziwe Yu: sample collection, processing, analysis and submission ------------ Data Tree ----------- | data collection summary.xlsx | Kinetic Trace Fitting.pxp | readme.txt | UV spectra.pxp | SEM.zip +---SEM | SEM1.tif | SEM2.tif | SEM3.tif | SEM4.tif | SERS Spectra Fitting.zip \---SERS Spectra Fitting 0223#16CTP_L1_AS1.pxp 0223#16CTP_L1_AS2.pxp 0223#16CTP_L1_S1.pxp 0223#16CTP_L1_S2.pxp 0223#16CTP_L2_AS1.pxp 0223#16CTP_L2_AS2.pxp 0223#16CTP_L2_S1.pxp 0223#16CTP_L2_S2.pxp 0223#16CTP_L3_AS1.pxp 0223#16CTP_L3_S1.pxp 0223#16CTP_L4_AS1.pxp 0223#16CTP_L4_S1.pxp 0223#17PTP_L1_AS1.pxp 0223#17PTP_L1_AS2.pxp 0223#17PTP_L1_S1.pxp 0223#17PTP_L1_S2.pxp 0223#17PTP_L2_AS1.pxp 0223#17PTP_L2_S1.pxp 0223#17PTP_L3_AS1.pxp 0223#17PTP_L3_AS2.pxp 0223#17PTP_L3_S1.pxp 0223#17PTP_L3_S2.pxp 0223#23NBT_L1_AS1.pxp 0223#23NBT_L1_S1.pxp 0223#24NBT_L1_AS1.pxp 0223#24NBT_L1_AS2.pxp 0223#24NBT_L1_S1.pxp 0223#24NBT_L1_S2.pxp 0223#24NBT_L2_AS1.pxp 0223#24NBT_L2_AS2.pxp 0223#24NBT_L2_S1.pxp 0223#24NBT_L2_S2.pxp 0223#28BT_L1_AS1.pxp 0223#28BT_L1_AS2.pxp 0223#28BT_L1_S1.pxp 0223#28BT_L1_S2.pxp 0223#28BT_L2_AS1.pxp 0223#28BT_L2_AS2.pxp 0223#28BT_L2_S1.pxp 0223#28BT_L2_S2.pxp 0223#28BT_L3_AS1.pxp 0223#28BT_L3_AS2.pxp 0223#28BT_L3_S1.pxp 0223#28BT_L3_S2.pxp 0223#30MTP_L1_AS1.pxp 0223#30MTP_L1_AS2.pxp 0223#30MTP_L1_S1.pxp 0223#30MTP_L1_S2.pxp 0223#30MTP_L2_AS1.pxp 0223#30MTP_L2_AS2.pxp 0223#30MTP_L2_S1.pxp 0223#30MTP_L2_S2.pxp 0223#30MTP_L3_AS1.pxp 0223#30MTP_L3_AS2.pxp 0223#30MTP_L3_S1.pxp 0223#30MTP_L3_S2.pxp 1013#3NBT_L1_AS1.pxp 1013#3NBT_L1_AS2.pxp 1013#3NBT_L1_S1.pxp 1013#3NBT_L1_S2.pxp 1013MTP_L1_AS1.pxp 1013MTP_L1_AS2.pxp 1013MTP_L1_S1.pxp 1013MTP_L1_S2.pxp