README file
Data Set Title: “Data for the characterization of the hemithioindigo photoswitches and its derivatives with X-ray photoabsorption and photoemission spectroscopies”
Data Set Author/s: 
Nenov Artur (Unibo), ORCID (0000-0003-3071-5341); 

Data Set Contributor/s: 
Nenov Artur (University of Bologna), ORCID 0000-0003-3071-5341;
Vozzi Caterina (CNR-IFN), ORCID 0000-0002-0212-0191;
Faccialà Davide (CNR-IFN), ORCID 0000-0002-5072-0394;
Oberti Linda (CNR-IFN), ORCID 0009-0007-6613-0245;

Data Set Contact Person/s: 
Nenov Artur (University of Bologna), ORCID 0000-0003-3071-5341, artur.nenov@unibo.it;
Oberti Linda (CNR-IFN), ORCID 0009-0007-6613-0245, linda.oberti@polimi.it;

Data Set License: this data set is distributed under a Creative Commons Attribution-NonCommercial (CC BY-NC), https://creativecommons.org/licenses/by-nc/4.0/deed.en 

Data Set DOI:
https://10.6092/unibo/amsacta/8038

Funding information:
This dataset is part of the project HAPPY - Understanding the Photochemistry of Sulfursubstituted DNA Bases by Advanced Ultrafast Spectroscopy, funded by Italian Ministry of University and Research (MUR) as part of the PRIN 2022 PNRR programme.

Publication Year: 2025
Data set Contents
The data set consists of:
•	Archive with computational data on HTI-H 
“HTI-H.zip”
•	Archive with computational data on HTI-OMe 
“HTI-OMe.zip”
•	Archive with computational data on HTI-SMe
“HTI-SMe.zip”
•	Archive with experimental spectra on HTI-H, HTI-OMe and HTI-SMe 
“EXP_SPECTRA.zip”
•	README file 
“READMEfile.rtf”
Data set Documentation
Abstract
The data set contains experimental and computational raw data of the near-edge x-ray absorption fine structure (NEXAFS) and x-ray photoemission spectra (XPS) at the K-edges of carbon and oxygen, as well as at the L23 edge of sulfur of three systems – HTI-H (Hemithioindigo–hemistilbene), HTI-OMe and HTI-SMe (bearing a methoxy group (OMe) and a thiomethyl group (SMe), respectively) – presented and discussed in the paper “Characterization of the hemithioindigo photoswitches and its derivatives with X-ray photoabsorption and photoemission spectroscopies”, published in JCP, 162, 244202 (2025), doi: 10.1063/5.0271164. The experimental data contains raw spectra as well as polished spectra with the background subtracted. The computational data contains input and output files of the electronic structure calculations of the valence, core-ionized and core-excited manifolds of the three samples.

Content of the files: 
•	each of the three files HTI-H.zip, HTI-OMe.zip and HTI-SMe.zip contains following folder structure (differences are listed in the Notes)
o	HTI-H/OMe/SMe.png (bitmap image of the optimized geometry)
o	core-excited (computational data of NEXAFS spectra)
•	carbon_K-edge
•	ANO-R2_single_carbon (calculation run with basis set ANO-R2 for a single carbon and ANO-R1 for all other atoms)
o	C_[1-15]
•	valence.input (input file for computing valence excited states)
•	valence.out (output file)
•	core.input (input file for computing core-excited states)
•	core.out (output file)
•	core.RasOrb (molecular orbital file with optimized RASSCF orbitals)
•	core.rasscf.molden (molecular orbital file for visualization)
•	core.png (bitmap image file of the core orbital)
•	HOMO.png and LUMO.png (bitmap images of the HOMO and LUMO orbitals from the calculation of the core-excited states)
•	tdm.input (input file for computing transition dipole moments between valence and core-excited states)
•	tdm.out (output file)
•	local.LocOrb (molecular orbital file with localized core-orbitals)
•	cis-HTI-H/OMe/SMe_opt_C[1-15].xyz (Cartesian coordinates of geometry to use in all calculations)
•	WF_SS-??-RASPT2_TDM_S0.dat: (summary of the electronic structure of the core-excited states)
•	oxygen_K-edge
•	core (computational data of core-excited states)
o	core.input (input file for computing core-excited states)
o	core.out (output file)
o	core.RasOrb (molecular orbital file with optimized RASSCF orbitals)
o	core.rasscf.molden (molecular orbital file for visualization)
o	MO[1-18].png (bitmap images of the molecular orbitals of the active space)
o	cis-HTI-H/OMe/SMe.xyz (Cartesian coordinates of geometry to use in all calculations)
o	WF_SS-??-RASPT2_TDM_S0.dat: (summary of the electronic structure of the core-excited states)
•	valence (computational data of valence states)
o	valence.input (input file for computing valence excited states)
o	valence.out (output file)
o	valence.RasOrb (molecular orbital file with optimized RASSCF orbitals)
o	valence.rasscf.molden (molecular orbital file for visualization)
o	MO[1-18].png (bitmap images of the molecular orbitals of the active space)
o	cis-HTI-H/OMe/SMe.xyz (Cartesian coordinates of geometry to use in all calculations)
•	sulfur_K-edge
•	singlet (computational data of singlet core-excited states)
o	rasscf.input (input file for computing core-excited states at CASSCF level)
o	rasscf.out (output file)
o	rasscf.RasOrb (molecular orbital file with optimized RASSCF orbitals)
o	rasscf.rasscf.molden (molecular orbital file for visualization)
o	raspt2.input (input file for computing CASPT2 energy correction for core-excited states)
o	raspt2.out (output file)
o	tdm_noSOC.input (input for computing transition dipole moments between valence and core-excited states w/o spin-orbit coupling)
o	tdm_noSOC.out (output file)
o	cis-HTI-H/OMe/SMe.xyz (Cartesian coordinates of geometry to use in all calculations)
o	WF_SS-??-RASPT2_TDM_S0.dat: (summary of the electronic structure of the core-excited states)
•	triplet (computational data of triplet core-excited states)
o	rasscf.input (input file for computing core-excited states at CASSCF level)
o	rasscf.out (output file)
o	rasscf.RasOrb (molecular orbital file with optimized RASSCF orbitals)
o	rasscf.rasscf.molden (molecular orbital file for visualization)
o	raspt2.input (input file for computing CASPT2 energy correction for core-excited states)
o	raspt2.out (output file)
o	cis-HTI-H/OMe/SMe.xyz (Cartesian coordinates of geometry to use in all calculations)
•	tdm_SOC.input (input file for computing transition dipole moments between valence and core-excited states with spin-orbit effects)
•	tdm_SOC.out (output file)
•	cis-HTI-H/OMe/SMe.xyz (Cartesian coordinates of geometry to use in all calculations)
•	WF_Spin-adiab_??_TDM_vS0.dat (summary of the electronic structure of the core-excited states with spin-orbit effects)
•	MO_core[1-3].png (bitmap images of the three 2p sulfur core-orbitals in the active space )
•	MO[1-2].png (bitmap images of the two virtual orbitals in the active space)
o	core-ionized (computational data of NEXAFS spectra)
•	carbon_K-edge
•	ANO-R2_single_carbon (calculation run with basis set ANO-R2 for a single carbon and ANO-R1 for all other atoms)
o	C_[1-15]
•	valence.input (input file for computing valence excited states)
•	valence.out (output file)
•	core.input (input file for computing core-ionized states)
•	core.out (output file)
•	core.RasOrb (molecular orbital file with optimized RASSCF orbitals)
•	core.rasscf.molden (molecular orbital file for visualization)
•	core.png (bitmap image file of the core orbital)
•	HOMO.png and LUMO.png (bitmap images of the HOMO and LUMO orbitals from the calculation of the core-ionized states)
•	dyson.input (input file for computing Dyson intensities between valence and core-ionized states)
•	dyson.out (output file)
•	cis-HTI-H/OMe/SMe_opt_C[1-15].xyz (Cartesian coordinates of geometry to use in all calculations)
•	WF_SS-??-RASPT2_Dy_S0.dat: (summary of the electronic structure of the core-ionized states)
•	oxygen_K-edge
•	core.input (input file for computing core-ionized states)
•	core.out (output file)
•	core.RasOrb (molecular orbital file with optimized RASSCF orbitals)
•	core.rasscf.molden (molecular orbital file for visualization)
•	MO[1-18].png (bitmap images of the molecular orbitals of the active space)
•	valence.input (input file for computing valence excited states)
•	valence.out (output file)
•	valence.RasOrb (molecular orbital file with optimized RASSCF orbitals)
•	valence.rasscf.molden (molecular orbital file for visualization)
•	cis-HTI-H/OMe/SMe.xyz (Cartesian coordinates of geometry to use in all calculations)
•	WF_SS-??-RASPT2_Dy_S0.dat: (summary of the electronic structure of the core-excited states)
•	sulfur_K-edge
•	doublet.input (input file for computing core-ionized states)
•	doublet.out (output file)
•	doublet.RasOrb (molecular orbital file with optimized RASSCF orbitals)
•	doublet.rasscf.molden (molecular orbital file for visualization)
•	MO_core[1-19].png (bitmap images of the active space molecular orbitals)
•	dyson_noSOC.input (input for computing Dyson intensities between valence and core-ionized states w/o spin-orbit coupling)
•	dyson_noSOC.out (output file)
•	dyson_SOC.input (input file for computing Dyson intensities between valence and core-intensities states with spin-orbit effects)
•	dyson_SOC.out (output file)
•	valence.input (input file for computing valence excited states)
•	valence.out (output file)
•	valence.RasOrb (molecular orbital file with optimized RASSCF orbitals)
•	cis-HTI-H/OMe/SMe.xyz (Cartesian coordinates of geometry to use in all calculations)
•	WF_Spin-adiab_??_TDM_vS0.dat (summary of the electronic structure of the core-excited states with spin-orbit effects)
o	optimization (contains data regarding the geometry optimization of the ground state geometry at the MP2 level
•	cis-HTI-H.xyz (initial guess of the geometry)
•	molcas_opt_mp2.input (input file)
•	molcas_opt_mp2.out (output file)
•	molcas_opt_mp2.Opt.xyz (Cartesian coordinates of optimized geometry)
•	molcas_opt_mp2.geo.molden (Cartesian coordinates of intermediate geometries of the optimization)
•	file EXP_SPECTRA.zip contains two series of data
o	raw data
o	background subtracted data
Both series contain NEXAFS and XPS spectra of HTI-H, HTI-OMe and HTI-SMe at the K-edges of carbon and oxygen, as well as at the L23 edge of sulfur
•	…

File specifics
•	Following a list of files’ extension and ways to edit / run / visualize content
o	.input: ASCII input files for performing electronic structure calculations which can be visualized with any text editor; calculations are to be executed with OpenMolcas (https://gitlab.com/Molcas/OpenMolcas/) 
o	.out: ASCII files with the outputs of the electronic structure calculations which can be visualized with any text editor;
o	WF...dat: ASCII files with summary of the electronic structure calculations which can be visualized with any text editor;
o	.RasOrb: ASCII files with molecular orbital coefficients, a necessary input for running CASSCF calculation with OpenMolcas 
o	.rasscf.molden: ASCII files which can be opened for visualizing molecular orbitals with Pegamoid (https://pypi.org/project/Pegamoid/) or with with Molden (https://www.theochem.ru.nl/molden/) 
o	.png: bitmap images of geometries and molecular orbitals that can be opened with any bitmap viewer
o	.xyz and geo.molden: Cartesian coordinates of geometries which can be opened with Molden (https://www.theochem.ru.nl/molden/) 
•	Each file in EXP_SPECTRA.zip has following format: two column ASCII file with “,” separator, 1st column: energy range (units: eV); 2nd column: intensity (arb. units)

Notes 
•	The carbon labels (C1-C15) in the carbon K-edge folders differ from the ones used in the paper.
•	The HTI-H data set contains an additional folder inside the folders core-excited/carbon_K-edge and core-ionized/carbon_K-edge named ANO-R2_all. It has the same structure and content as the folder ANO-R2_single_carbon and contains benchmark computations with basis set ANO-R2 on all carbons
•	The HTI-OMe and HTI-SMe data sets contain core-excited and core-ionized calculations at the carbon K-edge only for carbons with labels C2, C5, C6, C12, C15 and C_CH3
•	The HTI-OMe data set contains neither core-excited not core-ionized data at the sulfur L-edge
•	The HTI-OMe data set contains separate core-excited and core-ionized data sets for the two oxygens named O1 (carbonyl) and O2 (methoxy)
•	The HTI-SMe data set contains separate core-excited and core-ionized data sets for the two sulfurs named S1 (benzothiophene) and S2 (thiomethyl)

Methodologies 
•    The simulated XPS and NEXAFS spectra presented in the main article can be obtained from the computational data in this data set by means of eqs. 1 and 2 from the main article. For convenience, binding energies and Dyson intensities, required to simulate the XPS spectra, as well as transition energies and transition dipole moments, required to simulate NEXAFS spectra, have been extracted from the calculations and can be found in the WF_Spin-adiab_??_TDM_vS0.dat and WF_SS-??-RASPT2_Dy_S0.dat files (the symbol “??” Indicates a variable number of states). Additional parameters (broadenings and shifts) are listed in the paper for each spectroscopy and edge.
•   The background subtraction in the experimental spectra was performed according to the protocol outlines in sec. I of the Supplementary Information