Computational Modelling of Singlet Fission: From the static picture to fission dynamics

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REPORT SULLE ATTIVITÀ SVOLTE

REPORT ON THE ACTIVITIES UNDERTAKEN

Corso di dottorato / PhD Program _European Joint Doctorate Programme in Theoretical

Chemistry and Computational Modelling_

Curriculum (se previsto / if applicable) _2015-2018_

Cognome / Family Name _Wibowo_

Nome / Name _Meilani Kurniawati_

Data nascita / Date of Birth _19 May 1989_

Luogo nascita / Place of Birth _Surabaya, Indonesia_

Data di rilascio del titolo / Date of issue of the certificate ________________________

Eventuale valutazione (se prevista) / Subsequent evaluation (if applicable) ___________________

Supervisori / Supervisors _Prof. Maurizio Persico and Prof. Giovanni Granucci (University of

Groningen), Prof. Ria Broer and Dr. Remco W.A. Havenith (University of Groningen)_

Commissione di esame finale (Nome, cognome e ente di afferenza) / Final exam board (Name,

Family Name and relevant department) ______________________________________________

ATTIVITÀ FORMATIVE / FORMATIVE ACTIVITIES

I anno di corso / I course year (anno accademico / academic year _2015/2016_) DENOMINAZIONE DEL CORSO / NAME OF THE COURSE DURATA / DURATION (in ore / in hours) SEDE / LOCATION (indicare Università o altra sede di svolgimento / indicate the university or other course location) DOCENTE / PROFESSOR (nome e cognome / name and family name) VOTAZIONE / FINAL MARK GIUDIZIO / EVALUATION LINGUA UTILIZZATA (italiano, inglese, altra lingua / Italian, English or other languages) Corsi del dottorato frequentati/ Doctorate courses attended Core Course of ITN-EJD-TCCM 80 Autonomous University of Madrid Team - English BSC Parallel Computing School 40 Barcelona Supercomputing Center Team - English TCCM Tutorial on

ADF 40 Vrije Universiteit Amsterdam Team - English Altri corsi/ Other

courses Dutch Course Level 1 120 University of Groningen Team - Dutch Science Integrity

Course 2 University of Groningen Team - English Mastering Your

PhD 8 University of Groningen Team - English Dutch Course

Level 2

120 University of Groningen

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2 Teaching for PhD 120 University of

Groningen Team - English

Seminari di ricerca/Research seminars (argomento e ore di svolgimento / topic and number of hours carried out) - II anno di corso / II course year (anno accademico / academic year _2016/2017_) DENOMINAZIONE DEL CORSO / NAME OF THE COURSE DURATA / DURATION (in ore / in hours) SEDE / LOCATION (indicare Università o altra sede di svolgimento / indicate the university or other course location) DOCENTE / PROFESSOR (nome e cognome / name and family name) VOTAZIONE / FINAL MARK GIUDIZIO / EVALUATION LINGUA UTILIZZATA (italiano, inglese, altra lingua / Italian, English or other languages) Corsi del Dottorato frequentati/ Doctorate Courses Attended SHARC and Excited State Dynamics Tutorial 40 University of

Vienna Team - English

School of Scientific Visualization for Chemistry 40 CINECA Supercomputer Applications and Innovation Team - English Project Management Course 12 Maria Theresia College, KU Leuven Team - English Altri corsi/ Other Courses Publishing in English 120 University of Groningen Team - English Seminari di ricerca/Research Seminars (argomento e ore di svolgimento / topic and number of hours carried out) - PERIODO DI SVOLGIMENTO (da ___ a ____ / a ___ to ___) ENTE OSPITANTE (nome, luogo ed eventuale supervisore / name, location and subsequent supervisor) ATTIVITÀ SVOLTE E RISULTATI ACTIVITIES CARRIED OUT AND RESULTS Esperienze di ricerca presso altre strutture / Research experience in other institutions 15 March 2017 – 15 June 2017 SIMUNE Atomistic Simulations, San Sebastián - Spain Performing periodic boundary calculations using SIESTA and testing the performance of the van der Waals functionals implemented in SIESTA. III anno di corso / III course year (anno accademico / academic year _2017/2018_)

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3 DEL CORSO / NAME OF THE COURSE DURATION (in ore / in hours) LOCATION (indicare Università o altra sede di svolgimento / indicate the university or other course location) PROFESSOR (nome e cognome / name and family name) / FINAL MARK GIUDIZIO / EVALUATION UTILIZZATA (italiano, inglese, altra lingua / Italian, English or other languages) Corsi del Dottorato frequentati/ Doctorate Courses Attended European Summer School in Quantum Chemistry

80 Sicily Team - English

ZCAM Course 40 Zaragoza Team - English

Altri corsi/ Other

Courses Italian Course Level 1.2 120 University of Pisa Team - Italian Seminari di ricerca/Research Seminars (argomento e ore di svolgimento / topic and number of hours carried out) -

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TITOLO DELLA TESI / TITLE OF THE PHD THESIS

Title: Computational Modelling of Singlet Fission Subtitle: From the static picture to fission dynamics

PROGETTO DI RICERCA/RESEARCH PROJECT (descrivere sinteticamente / please provide a short

description)

Singlet fission, the conversion of an optically singlet excited state into a pair of two triplet excitons, which are coupled into an overall spin singlet, is one promising strategy to increase the efficiency of single junction solar cells beyond the theoretical limit. The renewed focus of this process driven by fundamental interests and its applications has become prominent. Experimental measurements and theoretical studies on the detailed mechanism through which the singlet fission occurs in pentacene, tetracene, and other polyacenes derivatives have been done intensively. Nevertheless, singlet fission is still a rare and not fully understood phenomenon in other chromophores. The aim of the research presented here is to understand the singlet fission mechanism and dynamics of recently proposed potential singlet fission chromophores, namely the bis(inner salt) of 2,5-dihydroxy-1,4-dimethyl-pyrazinium (DHDMPY) and 2,5-bis(fluorene-9-ylidene)-2,5-dihydrothiophene (ThBF), with the aid of theoretical chemistry and computational modelling. First, static quantum chemical calculations based on the nonorthogonal configuration interaction approach were performed to calculate effective electronic couplings of pairs of DHDMPY molecules, followed by a preliminary exploration of its crystal structure and dynamics. The resulting couplings showed that DHDMPY is indeed a potential singlet fission chromophore. Second, nonadiabatic dynamics simulations were performed based on the trajectory surface hopping approach with ‘on-the-fly’ calculations of electronic wave functions and energies by the semiempirical floating occupation molecular orbital—configuration interaction method. The aim was to investigate the fission dynamics of a pair of ThBF molecules embedded in their crystal environment and to predict the excited state lifetimes and the singlet fission quantum yield. It turned out that the process is fast, being almost complete in few picoseconds, and the quantum yield is very high.

CONVEGNI, WORKSHOP E SEMINARI IN ITALIA E ALL’ESTERO/ CONFERENCES, WORKSHOPS,

SEMINARSATTENDED IN ITALY AND ABROAD (indicare denominazione, sede, data e se la

partecipazione ha previsto anche la presentazione di un contributo / please provide the name, the

location, the date and whether the participation included also the presentation of a contribution)

1. CHAINS (Chemistry As Innovating Science), the Dutch chemistry conference, Meilani Wibowo, María Izquierdo, Ria Broer, and Remco W. A. Havenith, Veldhoven, the Netherlands, 30 November – 2 December 2015, poster contribution: Computational approaches to study materials for higher efficiency organic photovoltaics. 2. Singlet Fission Workshop, Peaceful Valley Ranch and Conference Center, Lyons, Colorado, USA, 18–21 June 2016, oral contribution: Nonorthogonal configuration interaction for the study of singlet fission. 3. 10th_{Congress on Electronic Structure: Principles and Applications ESPA 2016, Mercedes Rubio, Meilani} Wibowo, Antonio Mas, and Daniel Roca-Sanjuán, Castellón de la Plana, Spain, 28 June – 1 July 2016, poster contribution: Spectroscopic and Photophysical Properties of Porphycene: A RASPT2 Study. 4. 1st_{Annual Workshop ITN-EJD-TCCM, Université Pierre et Marie Curie, Paris, France, 18–20 July 2016,}

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5 oral and poster contributions: Nonorthogonal configuration interaction for the calculation of singlet fission rate. 5. CHAINS (Chemistry As Innovating Science), the Dutch chemistry conference, Veldhoven, the Netherlands, 6–8 December 2016, oral contribution: Nonorthogonal configuration interaction for calculating singlet fission efficiency. 6. Next-Gen III: PV Materials, Meilani Wibowo, Ria Broer, and Remco W. A. Havenith, Oosterpoort, Groningen, the Netherlands, 2–5 July 2017, poster contribution: Elucidation of the singlet fission mechanism: A theoretical study. 7. Chemistry for the Future 2017, Pisa, Italy, 5–7 July 2017, oral contribution: Elucidation of the singlet fission mechanism: A theoretical study. 8. 2nd_{Annual Workshop ITN-EJD-TCCM, Maria Theresia College, KU Leuven, Belgium, 17–19 July 2017, oral} and poster contributions: Electronic coupling calculations for a potential singlet fission chromophore. 9. WATOC2017, Meilani Wibowo, Ria Broer, Maurizio Persico, and Remco W. A. Havenith, Munich, Germany, 27 August – 1 September 2017, poster contribution: Electronic coupling and crystal structure calculations for potential singlet fission chromophores. 10. PPES2018 – Photoinduced Processes in Embedded Systems, Meilani Wibowo, Giovanni Granucci, Maurizio Persico, Pisa, Italy, 24–27 June 2018, poster contribution: Resolving the singlet fission dynamics at QM/MM level. 11. Chemistry for the Future 2018, Pisa, Italy, 4–6 July 2018, oral contribution: Elucidation of singlet fission dynamics by trajectory surface hopping simulations. 12. 3rd_{Annual Workshop ITN-EJD-TCCM, Dipartimento di Chimica e Chimica Industriale, Università di Pisa,} Pisa, Italy, 23–25 July 2018, oral and poster contributions: Nonadiabatic dynamics simulations for understanding the singlet fission mechanism in thienoquinoidal molecule.

EVENTUALE ATTIVITÀ DI RICERCA IN AZIENDA / SUBSEQUENT RESEARCH ACTIVITIES IN

COMPANIES (indicare denominazione, ente ospitante, periodo e luogo di svolgimento, eventuale

supervisore aziendale, attività svolte e risultati / please indicate the name, the hosting institution,

the period and duration of the activity, the subsequent company supervisor, activities carried out

and results)

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PUBBLICAZIONI (N.B. depositate in ARPI) / PUBLICATIONS (Note: Publications must be stored in

ARPI

TIPOLOGIA PUBBLICAZIONE (articolo, proceeding, monografia, edizione fonti…) TYPOLOGY (article, proceeding, monography, source edition…) ALTRI AUTORI

COAUTHORS PUBBLICAZIONE TITOLO DELLA TITLE ESTREMI DELLA PUBBLICAZIONE (rivista, editore, convegno, altro) PUBLICATION DETAILS (journal title, publishing company, conference title and so on) ISSN/ISBN Article Meilani Wibowo, Maurizio Persico, and Giovanni Gran Nonadiabatic dynamics simulations of singlet fission in 2,5-bis(fluorene- 9-ylidene)-2,5-dihydrothiophene crystals Physical Chemistry Chemical Physics 2019, 21, 692-701 - Article Meilani Wibowo, Ria Broer, and Remco W. A. Havenith A rigorous nonorthogonal configuration interaction approach for the calculation of electronic couplings between diabatic states applied to singlet fission Computational and Theoretical Chemistry 2017, 1116, 190-194 - Article Marco Garazzi*, Meilani Wibowo*, Hugo Gattuso, Elise Dumont, Daniel Roca-Sanjuán, and Antonio Monari (*contributed equally) Hydrogen abstraction by photoexcited benzophenone: consequences for DNA photosensitization Physical Chemistry Chemical Physics 2016, 18, 7829-7836 - Article Elise Dumont, Meilani Wibowo, Daniel Roca-Sanjuán, Marco Garavelli, Xavier Assfeld, and Antonio Monari Resolving the benzophenone DNA-photosensitization mechanism at QM/MM level Journal of Physical Chemistry Letter 2015, 6, 576-580 -

PUBBLICAZIONI (in corso di pubblicazione) / PUBLICATIONS (submitted but not yet published)

TIPOLOGIA PUBBLICAZIONE (articolo, proceeding, monografia, edizione fonti…) TYPOLOGY: ( article, proceeding, monography, source edition…) ALTRI AUTORI

/ COAUTHORS PUBBLICAZIONE TITOLO DELLA TITLE ESTREMI DELLA PUBBLICAZIONE (rivista, editore, convegno, altro) PUBLICATION DETAILS (journal title, publishing company, conference title and so on) -

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ATTIVITÀ DI TUTORAGGIO E DIDATTICA INTEGRATIVA / TUTORING AND SUPPLEMENTARY

TEACHING ACTIVITIES

April 2016 - June 2016: teaching assistant in the computer lab/practicum of the Quantum Chemistry course for bachelor students and Computational Quantum Chemistry course for master students at the University of Groningen.

ALTRO / OTHER ACTIVITIES

1. Writing an Introductory Essay (the first 6 months of the PhD programme at the University of Groningen, 16 September 2015 - 3 March 2016). 2. October 2015 - September 2016: the first year editors of the Young Researchers Forum – European Joint Doctorate Newsletter. 3. Active member of the Marie Curie Alumni and EURAXESS ASEAN (since November 2016). 4. Writing an article about Women in Science and the importance of mobility in the EURAXESS ASEAN Newsletter. 5. Attended the FOM Focus Scientific Meeting (http://www.groningensolar.nl/about), Zernike Institute for Advanced Materials, University of Groningen, the Netherlands from October 2015 until March 2017. During this period, she presented her research project two times, on 8 February 2017 and 15 June 2016. This meeting aims to deliver the current state of on-going projects of each research line (materials, OPV device physics and modelling, theoretical chemistry and spectroscopy). In this meeting, one member presents his/her on-going research and the other members (experimentalists, device physicists, engineers, and theoreticians) give their ideas, comments, and/or suggestions. 6. Attended the trimonthly Berendsen Centre for Multiscale Modelling and Molecular Design meetings (http://www.rug.nl/research/zernike/berendsen-center/), University of Groningen, the Netherlands from October 2015 until March 2017. She presented her research project as a representative from the Theoretical Chemistry Group on 20 September 2016. In this meeting, the participating research groups (Theoretical Chemistry, Theory of Condensed Matter, Micromechanics and Molecular Dynamics) discuss on-going science and organise (inter)national meetings on multiscale modelling and computational design. 7. Attended the ‘Passion for Knowledge’ festival in San Sebastian from 27 September to 1 October 2016, which aims to promote science as a cultural key activity. In this festival, she attended the public lectures held by established scientists and Nobel Laureates and the PhD outreach program activities: a. Meet the Professor A group of PhD students met Martin Karplus and Dudley Hershbach Nobel Laureates for discussing with them about science, curiosities and their life. b. Encounter with secondary school student PhD students met the secondary school students for sharing scientific and personal experiences related with TCCM PhD program. c. Dissemination paper for a blog PhD students wrote a dissemination paper about their thesis project on Mapping Ignorance blog.