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\title{A Mountaineering Strategy to Excited States: Highly-Accurate Energies and Benchmarks for Exotic Molecules and Radicals\\Supporting Information}

\author{Pierre-Fran{\c c}ois Loos}
	\email{loos@irsamc.ups-tlse.fr}
	\affiliation[LCPQ, Toulouse]{Laboratoire de Chimie et Physique Quantiques, Universit\'e de Toulouse, CNRS, UPS, France}
\author{Anthony Scemama}
	\affiliation[LCPQ, Toulouse]{Laboratoire de Chimie et Physique Quantiques, Universit\'e de Toulouse, CNRS, UPS, France}
\author{Martial Boggio-Pasqua}
	\affiliation[LCPQ, Toulouse]{Laboratoire de Chimie et Physique Quantiques, Universit\'e de Toulouse, CNRS, UPS, France}
\author{Denis Jacquemin}
	\email{Denis.Jacquemin@univ-nantes.fr}
	\affiliation[UN, Nantes]{Laboratoire CEISAM - UMR CNRS 6230, Universit\'e de Nantes, 2 Rue de la Houssini\`ere, BP 92208, 44322 Nantes Cedex 3, France}    


\begin{document}

\clearpage

\section{Basis set and frozen-core effects}

\begin{sidewaystable}[htp]
\scriptsize
\caption{CC3 transition energies (in eV) determined with various basis sets. FC, SC, and full stand for frozen-core (large cores), small-core (freezing only the $1s$ electrons) and correlating all electrons, respectively.}
\label{Table-S1}
\begin{tabular}{cc|cccccccc}
\hline 
			&	&{\Pop} 	& {\AVDZ}		& {\AVTZ}		& {\AVQZ}		& {\AVQZ}	& {\AVQZ}		& {\ACVQZ}& {\AVPZ}\\
			&	&FC 		& FC			& FC			& FC			& SC		&	 Full		& Full	& FC \\
\hline
Carbonylfluoride& $^1A_2$	&7.33	&7.34	&7.31	&7.31	&		&7.29	&7.28	&7.31\\
			& $^3A_2$	&7.03	&7.05	&7.03	&7.03	&		&7.01	&7.00	&7.04\\
CCl$_2$		& $^1B_1$	&2.71	&2.69	&2.61	&2.60	&2.59	&2.57	&2.57	&2.59\\
			& $^1A_2$	&4.46	&4.40	&4.35	&4.37	&4.36	&4.34	&4.33	&4.36\\
			& $^3B_1$	&1.10	&1.20	&1.20	&1.21	&1.21	&1.19	&1.19	&1.21\\
			& $^3A_2$	&4.41	&4.34	&4.28	&4.30	&4.29	&4.28	&4.26	&4.29\\
CClF			& $^1A''$		&3.66	&3.63	&3.56	&3.55	&3.55	&3.53	&3.53	&3.55\\
CF$_2$		& $^1B_1$	&5.18	&5.12	&5.07	&5.06	&		&5.02	&5.02	&5.05\\
			& $^3B_1$	&2.71	&2.71	&2.76	&2.77	&		&2.75	&2.75	&2.77\\
Difluorodiazirine&$^1B_1$	&3.83	&3.80	&3.74	&3.73	&		&&&\\
			&$^1A_2$		&7.13	&7.11	&7.02	&7.00	&		&&&\\
			&$^1B_2$		&8.51	&8.45	&8.50	&8.52	&		&&&\\
			&$^3B_1$		&3.09	&3.06	&3.03	&3.03	&		&&&\\
			&$^3B_2$		&5.48	&5.47	&5.45	&5.47	&		&&&\\
			&$^3B_1$		&5.86	&5.83	&5.81	&5.82	&		&&&\\
Formylfluoride	& $^1A''$		&6.09	&6.03	&5.99	&5.99	&		&5.98	&5.97	&6.00\\
			& $^3A''$		&5.72	&5.65	&5.62	&5.63	&		&5.62	&5.61	&5.64\\
HCCl		& $^1A''$		&2.05	&2.02	&1.97	&1.96	&1.96	&1.95	&1.94	&1.96\\
HCF			&$^1A''$		&2.58	&2.53	&2.49	&2.49	&		&2.47	&2.47	&2.49\\
HCP			& $^1\Sigma^-$	&5.19	&5.06	&4.85	&4.83	&4.83	&4.82	&4.81	&4.82\\
			& $^1\Delta$	&5.48	&5.33	&5.15	&5.12	&5.11	&5.11	&5.09	&5.10\\
			& $^3\Sigma^+$&3.44	&3.47	&3.45	&3.46	&3.46	&3.46	&3.44	&3.47\\
			& $^3\Delta$	&4.40	&4.35	&4.22	&4.21	&4.21	&4.20	&4.20	&4.20\\
HPO			& $^1A''$		&2.49	&2.47	&2.46	&2.47	&2.47	&2.47	&2.47	&2.48\\
HPS			& $^1A''$		&1.57	&1.60	&1.59	&1.60	&1.59	&1.59	&1.59	&1.61\\
HSiF			& $^1A''$		&3.09	&3.08	&3.07	&3.07	&3.06	&3.06	&3.06	&3.07\\
SiCl$_2$		&$^1B_1$		&3.94	&3.93	&3.90	&3.91	&3.91	&3.91	&3.90	&3.92\\
			&$^3B_1$		&2.39	&2.45	&2.48	&2.49	&2.52	&2.52	&2.52	&2.50\\
Silylidene		&$^1A_2$		&2.14	&2.18	&2.15	&2.16	&2.15	&2.16	&2.15	&2.16\\
			&$^1B_2$		&3.88	&3.81	&3.78	&3.79	&3.78	&3.78	&3.78	&3.80\\
\hline																			
\end{tabular}
\vspace{-0.3 cm}
\begin{flushleft}
\end{flushleft}
\end{sidewaystable}

\clearpage
\begin{figure}[htp]
  \includegraphics[scale=1.05,viewport=2.8cm 22.3cm 18.3cm 27.5cm,clip]{Figure-S1.pdf}
  \caption{Histograms of the error distribution (in eV) obtained by comparing the CC3 transitions obtained with three basis set to the corresponding CC3/{\AVQZ} values
  for the data listed in Table \ref{Table-S1}. Note the different $Y$ scales.}
  \label{Fig-S1}
\end{figure}


\begin{figure}[htp]
  \includegraphics[scale=1.05,viewport=2.8cm 22.3cm 18.3cm 27.5cm,clip]{Figure-S2.pdf}
  \caption{Histograms of the error distribution (in eV) obtained by comparing the CCSDT transitions obtained with three basis set to the corresponding CCSDT/{\AVQZ} values
  for the data listed in Table 3 of the main text. Note the different $Y$ scales.}
  \label{Fig-S2}
\end{figure}



\clearpage

\section{Benchmark data}
\begin{sidewaystable}[htp]
\scriptsize
\caption{Transition energies determined with various models for the exotic set. All values are in eV and have been obtained with the  {\AVTZ} basis set applying the FC approximation.}
\label{Table-S2}
\begin{tabular}{cc|c|ccccccccccccccc}
\hline 
			&			&TBE		& \rotatebox{90}{CIS(D)} & \rotatebox{90}{CC2} & \rotatebox{90}{EOM-MP2} & \rotatebox{90}{STEOM-CCSD} & \rotatebox{90}{CCSD} & \rotatebox{90}{CCSDR(3)} & 
			\rotatebox{90}{CCSDT-3} & \rotatebox{90}{CC3} &  \rotatebox{90}{SOS-ADC(2) [TM]}  &  \rotatebox{90}{SOS-CC2 [TM]} &  \rotatebox{90}{SCS-CC2 [TM]} &  \rotatebox{90}{SOS-ADC(2) [QM]} & \rotatebox{90}{ADC(2)} 
			 & \rotatebox{90}{ADC(3)}  & \rotatebox{90}{ADC(2.5)} \\
\hline
Carbonylfluoride& $^1A_2$	&7.31	&7.38	&7.47	&7.39	&7.07	&7.36	&7.32	&7.32	&7.31	&7.27	&7.48	&7.47	&7.04	&7.22	&7.32	&7.27\\
			& $^3A_2$	&7.06	&7.08	&7.14	&7.08	&6.82	&7.03	&		&		&7.03	&7.05	&7.24	&7.21	&6.81	&6.91	&7.01	&6.96\\
CCl$_2$		& $^1B_1$	&2.59	&2.59	&2.58	&2.36	&2.35	&2.61	&2.59	&2.61	&2.61	&2.58	&2.67	&2.64	&2.44	&2.46	&2.41	&2.44\\
			& $^1A_2$	&4.40	&4.20	&4.27	&4.27	&4.33	&4.57	&4.37	&4.41	&4.35	&4.50	&4.61	&4.50	&4.29	&4.12	&4.76	&4.44\\
			& $^3B_1$	&1.22	&1.09	&1.15	&0.84	&		&1.11	&		&		&1.20	&1.16	&1.27	&1.23	&1.06	&0.98	&0.91	&0.95\\
			& $^3A_2$	&4.31	&4.24	&4.20	&4.17	&4.23	&4.45	&		&		&4.28	&4.48	&4.59	&4.46	&4.29	&4.05	&4.62	&4.34\\	
CClF			& $^1A''$		&3.55	&3.56	&3.57	&3.34	&3.39	&3.57	&3.55	&3.56	&3.56	&3.54	&3.63	&3.61	&3.39	&3.44	&3.35	&3.40\\	
CF$_2$		& $^1B_1$	&5.09	&5.06	&5.09	&4.90	&4.90	&5.09	&5.07	&5.08	&5.07	&5.05	&5.15	&5.13	&4.89	&4.94	&4.86	&4.90\\
			& $^3B_1$	&2.77	&2.63	&2.70	&2.47	&2.61	&2.69	&		&		&2.76	&2.74	&2.84	&2.79	&2.64	&2.54	&2.48	&2.51\\
Difluorodiazirine&$^1B_1$	&3.74	&3.89	&3.74	&3.94	&3.56	&3.83	&3.76	&3.75	&3.74	&3.97	&3.97	&3.90	&3.77	&3.74	&3.52	&3.63\\
			&$^1A_2$		&7.00	&7.46	&7.19	&7.24	&		&7.10	&7.05	&7.02	&7.02	&7.29	&7.28	&7.25	&7.10	&7.19	&6.70	&6.95\\
			&$^1B_2$		&8.52	&8.53	&8.29	&8.90	&		&8.69	&8.55	&8.55	&8.50	&8.95	&8.82	&8.65	&8.77	&8.42	&8.50	&8.46\\
			&$^3B_1$		&3.03	&3.17	&3.03	&3.17	&2.91	&3.07	&		&		&3.03	&3.32	&3.33	&3.23	&3.14	&3.01	&2.77	&2.89\\
			&$^3B_2$		&5.44	&5.89	&5.77	&5.97	&		&5.40	&		&		&5.45	&5.53	&5.55	&5.63	&5.41	&5.72	&5.04	&5.38\\	
			&$^3B_1$		&5.80	&6.13	&5.99	&5.71	&5.59	&5.84	&		&		&5.81	&6.20	&6.21	&6.13	&6.05	&5.97	&5.47	&5.72\\
Formylfluoride	& $^1A''$		&5.96	&6.03	&6.14	&6.00	&5.88	&6.02	&5.99	&6.00	&5.99	&5.99	&6.19	&6.17	&5.78	&5.91	&5.93	&5.92\\	
			& $^3A''$		&5.73	&5.63	&5.70	&5.60	&5.51	&5.60	&		&		&5.62	&5.67	&5.85	&5.80	&5.48	&5.50	&5.54	&5.52\\
HCCl		& $^1A''$		&1.98	&1.95	&1.91	&1.65	&1.80	&1.99	&1.95	&1.98	&1.97	&2.01	&2.06	&2.01	&1.88	&1.84	&1.81	&1.83\\
HCF			&$^1A''$		&2.49	&2.54	&2.44	&2.19	&2.32	&2.51	&2.48	&2.50	&2.49	&2.51	&2.58	&2.53	&2.38	&2.34	&2.30	&2.32\\
HCP			& $^1\Sigma^-$	&4.84	&5.07	&5.07	&4.83	&4.90	&4.87	&4.85	&4.84	&4.85	&5.02	&5.07	&5.07	&4.91	&5.02	&4.37	&4.70\\
			& $^1\Delta$	&5.15	&5.40	&5.41	&5.12	&5.22	&5.16	&5.16	&5.14	&5.15	&5.23	&5.29	&5.33	&5.12	&5.33	&4.66	&5.00\\
			& $^3\Sigma^+$&3.47	&3.74	&3.73	&3.55	&3.41	&3.36	&		&		&3.45	&3.37	&3.38	&3.50	&3.30	&3.69	&3.10	&3.40\\
			& $^3\Delta$	&4.22	&4.44	&4.43	&4.23	&4.20	&4.17	&		&		&4.22	&4.47	&4.52	&4.49	&4.39	&4.39	&3.79	&4.09\\
HPO			& $^1A''$		&2.47	&2.54	&2.50	&2.44	&2.45	&2.54	&2.48	&2.48	&2.46	&2.57	&2.68	&2.62	&2.39	&2.35	&2.35	&2.35\\
HPS			& $^1A''$		&1.59	&1.68	&1.68	&1.39	&1.55	&1.67	&1.59	&1.60	&1.59	&1.74	&1.79	&1.75	&1.60	&1.62	&1.39	&1.51\\
HSiF			& $^1A''$		&3.05	&3.16	&3.14	&2.78	&3.02	&3.12	&3.07	&3.08	&3.07	&3.22	&3.24	&3.21	&3.12	&3.11	&2.88	&3.00\\
SiCl$_2$		&$^1B_1$		&3.91	&3.99	&3.99	&3.70	&3.80	&3.96	&3.89	&3.91	&3.90	&4.01	&4.04	&4.02	&3.89	&3.95	&3.76	&3.86\\
			&$^3B_1$		&2.48	&2.40	&2.39	&2.18	&		&2.45	&		&		&2.48	&2.51	&2.52	&2.48	&2.44	&2.35	&2.31	&2.33\\
Silylidene		&$^1A_2$		&2.11	&2.39	&2.37	&2.09	&2.21	&2.29	&2.16	&2.17	&2.15	&2.35	&2.35	&2.35	&2.24	&2.37	&1.87	&2.12\\
			&$^1B_2$		&3.78	&3.91	&3.85	&3.66	&3.81	&3.88	&3.79	&3.80	&3.78	&3.98	&3.94	&3.91	&3.87	&3.88	&3.40	&3.64\\
\hline																			
\end{tabular}
\vspace{-0.3 cm}
\begin{flushleft}
\end{flushleft}
\end{sidewaystable}


\begin{table}[htp]
\scriptsize
\caption{Transition energies determined with various models for the radical set. All values are in eV and have been obtained with the  {\AVTZ} basis set applying the FC approximation.}
\label{Table-S3}
\begin{tabular}{cc|c|cccc}
\hline 
			&			&TBE		& U-CCSD & RO-CCSD & U-CC3 & RO-CC3 \\
\hline
Allyl			&$^2B_1$		&3.39	&3.70	&3.48	&3.48	&3.44	\\
			&$^2A_1$		&4.99	&5.12	&5.01	&4.97	&4.95	\\
BeF			&$^2\Pi$		&4.14	&4.18	&4.18	&4.15	&4.15	\\
			&$^2\Sigma^+$	&6.21	&6.31	&6.31	&6.21	&6.21	\\
BeH			&$^2\Pi$		&2.49	&2.51	&2.51	&2.50	&2.50	\\
			&$^2\Pi$		&6.46	&6.47	&6.47	&6.46	&6.46	\\
BH$_2$		&$^2B_1$		&1.18	&1.20	&1.20	&1.19	&1.20	\\
CH			&$^2\Delta$	&2.91	&3.18	&3.17	&3.11	&3.10	\\
			&$^2\Sigma^-$	&3.29	&4.58	&4.39	&3.61	&3.55	\\
			&$^2\Sigma^+$	&3.98	&5.47	&5.36	&4.45	&4.40	\\
CH$_3$		&$^2A_1'$	&5.85	&5.89	&5.87	&5.86	&5.85	\\
			&$^2E'$		&6.96	&7.00	&6.98	&6.97	&6.97	\\
			&$^2E'$		&7.18	&7.21	&7.20	&7.19	&7.19	\\
			&$^2A_2''$	&7.65	&7.67	&7.66	&7.65	&7.65	\\
CN			&$^2\Pi$		&1.34	&1.56	&1.34	&1.40	&1.36	\\
			&$^2\Sigma^+$	&3.22	&3.54	&3.35	&3.31	&3.26	\\%CHECK
CNO			&$^2\Sigma^+$	&1.61	&2.24	&2.25	&1.75	&1.77	\\%CHECK
			&$^2\Pi$		&5.49	&5.68	&5.60	&5.52	&5.51	\\
CO$^+$		&$^2\Pi$		&3.28	&3.60	&3.29	&3.33	&3.29	\\
			&$^2\Sigma^+$	&5.81	&6.21	&6.02	&5.76	&5.68	\\
F$_2$BO		&$^2B_1$		&0.73	&0.74	&0.73	&0.71	&0.71	\\
			&$^2A_1$		&2.80	&2.84	&2.83	&2.79	&2.79	\\
F$_2$BS		&$^2B_1$		&0.51	&0.51	&0.49	&0.48	&0.48	\\
			&$^2A_1$		&2.99	&3.03	&3.01	&2.94	&2.93	\\
H$_2$BO		&$^2B_1$		&2.15	&2.14	&2.13	&2.17	&2.17	\\
			&$^2A_1$		&3.49	&3.53	&3.51	&3.52	&3.52	\\
HCO			&$^2A''$		&2.09	&2.14	&2.13	&2.10	&2.11	\\
			&$^2A'$		&5.45	&5.54	&5.53	&5.44	&5.44	\\
HOC			&$^2A''$		&0.92	&0.95	&0.93	&0.93	&0.93	\\
H$_2$PO		&$^2A''$		&2.80	&2.91	&2.91	&2.83	&2.83	\\
			&$^2A'$		&4.21	&4.26	&4.27	&4.21	&4.23	\\
H$_2$PS		&$^2A''$		&1.16	&1.18	&1.14	&1.16	&1.15	\\
			&$^2A'$		&2.72	&2.79	&2.77	&2.75	&2.75	\\
NCO			&$^2\Sigma^+$	&2.89	&3.04	&2.94	&2.94	&2.86	\\
			&$^2\Pi$		&4.73	&5.01	&5.02	&4.80	&4.81	\\
NH$_2$		&$^2A_1$		&2.12	&2.13	&2.12	&2.13	&2.12	\\
Nitromethyl	&$^2B_2$		&2.05	&2.47	&2.46	&2.06	&2.05	\\
			&$^2A_2$		&2.38	&2.71	&2.71	&2.47	&2.46	\\
			&$^2A_1$		&2.56	&2.94	&2.93	&2.56	&2.55	\\
			&$^2B_1$		&5.35	&5.59	&5.56	&5.38	&5.36	\\
NO			&$^2\Sigma^+$&6.13	&6.23	&6.21	&6.13	&6.12	\\
			&$^2\Sigma^+$	&7.29	&7.40	&7.38	&7.30	&7.28	\\
OH			&$^2\Sigma^+$	&4.10	&4.14	&4.13	&4.13	&4.13	\\
			&$^2\Sigma^-$	&8.02	&7.75	&7.76	&7.66	&7.66	\\
PH$_2$		&$^2A_1$		&2.77	&2.81	&2.78	&2.78	&2.77	\\
Vinyl			&$^2A''$		&3.26	&3.51	&3.35	&3.34	&3.30	\\
			&$^2A''$		&4.69	&4.91	&4.80	&4.76	&4.73	\\
			&$^2A'$		&6.20	&6.38	&6.32	&6.22	&6.24	\\
\hline																			
\end{tabular}
\vspace{-0.3 cm}
\begin{flushleft}
\end{flushleft}
\end{table}
			



\clearpage

\section{Multi-reference approaches for CON}



\begin{table}[htp]

\caption{Vertical transition energies (eV) of CON. All calculations using a full valence active space of (15e,12o) and the {\AVTZ} basis set. NEVPT2
calculations are performed within the partially-contracted scheme whereas CASPT2 calculations use a level shift of 0.3 a.u. and a IPEA of 0.25 a.u.}
\label{Table-S4}
\begin{tabular}{ccccccc}
\hline 
State		& Active space	& State-average	&	CASSCF	&	 NEVPT2	&	CASPT2	&	MRCI \\
		& ($a_1,b_1,b_2,a_2$) & ($A_1,B_1,B_2,A2$) \\
\hline
$^4\Pi(\pi\rightarrow\pi^\star)$		& (6,3,3,0)		& (0,2,2,0)		&3.01	&2.72	&2.74	&2.81\\
$^2\Pi(\pi\rightarrow\pi^\star)$		& (6,3,3,0)		& (0,2,2,0)		&3.94	&3.52	&3.55	&3.62\\
$^2\Sigma^+(n\rightarrow\pi^\star)$	& (6,3,3,0)		& (1,1,1,0)		&3.85	&3.81	&3.72	&3.83\\
$^2\Phi(\pi\rightarrow\pi^\star)$		& (6,3,3,0)		& (0,2,2,0)		&4.86	&4.32	&4.35	&4.44\\
\hline																			
\end{tabular}
\vspace{-0.3 cm}
\begin{flushleft}
\end{flushleft}
\end{table}


\clearpage
\section{Geometries}

\subsection{Exotic compounds}

Below, we provide the Cartesian coordinates of the exotic compounds investigated in this study. 
These are given in atomic units (bohr) and they have been obtained at the \CC{3}(full)/{\AVTZ} level of theory.

\subsubsection{Carbonylfluoride (F$_2$CO)}

\begin{singlespace}
\begin{verbatim}
C    0.00000000            0.00000000           -0.30652633
O    0.00000000            0.00000000           -2.52469534
F    0.00000000            2.00254958            1.16003038
F    0.00000000           -2.00254958            1.16003038
\end{verbatim}
\end{singlespace}

\subsubsection{CCl$_2$}

\begin{singlespace}
\begin{verbatim}
C    0.00000000            0.00000000           -1.60920674
Cl   0.00000000            2.65360612            0.27602958
Cl   0.00000000           -2.65360612            0.27602958
\end{verbatim}
\end{singlespace}

\subsubsection{CClF}

\begin{singlespace}
\begin{verbatim}
C    0.29776085            0.00000000            1.47969075
F    2.16980264            0.00000000           -0.10569879
Cl  -2.46756349            0.00000000           -0.32822320
\end{verbatim}
\end{singlespace}


\subsubsection{CF$_2$}
\begin{singlespace}
\begin{verbatim}
C    0.00000000            0.00000000           -1.14170749
F    0.00000000            1.94810617            0.36114458
F    0.00000000           -1.94810617            0.36114458
\end{verbatim}
\end{singlespace}


\subsubsection{Difluorodiazirine (CF$_2$N$_2$)}
\begin{singlespace}
\begin{verbatim}
C    0.00000000            0.00000000           -0.15283028
F    0.00000000            2.06077297           -1.57706828
F    0.00000000           -2.06077297           -1.57706828
N    1.20382241            0.00000000            2.20566821
N   -1.20382241            0.00000000            2.20566821
\end{verbatim}
\end{singlespace}


\subsubsection{Formylfluoride (FHCO)}
\begin{singlespace}
\begin{verbatim}
C    0.00536098            0.00000000            0.75320959
O    2.17369813            0.00000000            0.22287752
H   -0.83846350            0.00000000            2.62640974
F   -1.84051320            0.00000000           -0.99373750
\end{verbatim}
\end{singlespace}

\subsubsection{HCCl}

\begin{singlespace}
\begin{verbatim}
H   -1.88068369            0.00000000           -0.14323924
Cl   2.28559426            0.00000000           -0.43261163
C   -0.40491057            0.00000000            1.32161964         
\end{verbatim}
\end{singlespace}

\subsubsection{HCF}

\begin{singlespace}
\begin{verbatim}
C   -0.13561085            0.00000000            1.20394474
F    1.85493976            0.00000000           -0.27610752
H   -1.71932891            0.00000000           -0.18206846
\end{verbatim}
\end{singlespace}

\subsubsection{HCP}

\begin{singlespace}
\begin{verbatim}
H    0.00000000            0.00000000           -4.03090449
C    0.00000000            0.00000000           -2.01691641
P    0.00000000            0.00000000            0.91401621
\end{verbatim}
\end{singlespace}

\subsubsection{HPO}

\begin{singlespace}
\begin{verbatim}
H    0.31668637            0.00000000            0.14072725
P   -0.80573521            0.00000000            2.65136926
O    1.43391190            0.00000000            4.38886277
\end{verbatim}
\end{singlespace}

\subsubsection{HPS}

\begin{singlespace}
\begin{verbatim}
H   -2.56278959            0.00000000            2.36296006
P    0.09114182            0.00000000            1.82568543
S    0.07946992            0.00000000           -1.85778170
\end{verbatim}
\end{singlespace}

\subsubsection{HSiF}

\begin{singlespace}
\begin{verbatim}
Si  -0.06438136            0.00000000            1.67253150
F    2.24990164            0.00000000           -0.33928119
H   -2.18552027            0.00000000           -0.28748154
\end{verbatim}
\end{singlespace}

\subsubsection{SiCl$_2$}

\begin{singlespace}
\begin{verbatim}
Si    0.00000000            0.00000000           -1.78528322
Cl    0.00000000            3.04414528            0.71619419
Cl    0.00000000           -3.04414528            0.71619419
\end{verbatim}
\end{singlespace}

\subsubsection{Silylidene (H$_2$CSi)}

\begin{singlespace}
\begin{verbatim}
C    0.00000000            0.00000000           -2.09539928
Si   0.00000000            0.00000000            1.14992930
H    0.00000000            1.70929524           -3.22894481
H    0.00000000           -1.70929524           -3.22894481
\end{verbatim}
\end{singlespace}

\clearpage


\subsection{Radicals}

Below, we provide the Cartesian coordinates of the radical compounds investigated in this study. 
These are given in atomic units (bohr) and they have been obtained at the UCCSD(T)(full)/{\AVTZ} level of theory,
except when noted.

\subsubsection{Allyl (C$_3$H$_5$)}

\begin{singlespace}
\begin{verbatim}
C    0.00000000            0.00000000            0.83050732
C    0.00000000            2.30981224           -0.38722841
C    0.00000000           -2.30981224           -0.38722841
H    0.00000000            0.00000000            2.87547067
H    0.00000000            4.06036949            0.65560561
H    0.00000000           -4.06036949            0.65560561
H    0.00000000            2.41059890           -2.42703281
H    0.00000000           -2.41059890           -2.42703281
\end{verbatim}
\end{singlespace}

\subsubsection{BeF}

\begin{singlespace}
\begin{verbatim}
Be   0.00000000            0.00000000           -1.77936990 
F    0.00000000            0.00000000            0.79083149  
\end{verbatim}
\end{singlespace}

\subsubsection{BeH}

\begin{singlespace}
\begin{verbatim}
Be   0.00000000            0.00000000            0.25103976
H    0.00000000            0.00000000           -2.24485003
\end{verbatim}
\end{singlespace}


\subsubsection{BH$_2$}

\begin{singlespace}
\begin{verbatim}
B    0.00000000            0.00000000            0.14984923
H    0.00000000            2.01119016           -0.81846345
H    0.00000000           -2.01119016           -0.81846345
\end{verbatim}
\end{singlespace}

\subsubsection{CH}

\begin{singlespace}
\begin{verbatim}
C    0.00000000            0.00000000           -0.16245872
H    0.00000000            0.00000000            1.93436816
\end{verbatim}
\end{singlespace}

\subsubsection{CH$_3$}

\begin{singlespace}
\begin{verbatim}
C    0.00000000            0.00000000            0.00000000
H    0.00000000            0.00000000            2.03379507
H    0.00000000            1.76131924           -1.01689753
H    0.00000000           -1.76131924           -1.01689753
\end{verbatim}
\end{singlespace}

\subsubsection{CN}

\begin{singlespace}
\begin{verbatim}
C    0.00000000            0.00000000           -1.18953886
N    0.00000000            0.00000000            1.01938091
\end{verbatim}
\end{singlespace}


\subsubsection{CNO}

\begin{singlespace}
\begin{verbatim}
C    0.00000000            0.00000000           -2.50680714
N    0.00000000            0.00000000           -0.22402176
O    0.00000000            0.00000000            2.07682752
\end{verbatim}
\end{singlespace}


\subsubsection{CON}

Optimized at the U-CCSDT/cc-pVTZ level.
\begin{singlespace}
\begin{verbatim}
C    0.00000000            0.00000000           -2.44062558
O    0.00000000            0.00000000           -0.20455596
N    0.00000000            0.00000000            2.32515818
\end{verbatim}
\end{singlespace}

\clearpage 
\subsubsection{CO$^+$}

\begin{singlespace}
\begin{verbatim}
C    0.00000000            0.00000000           -1.20324172
O    0.00000000            0.00000000            0.90271821
\end{verbatim}
\end{singlespace}

\subsubsection{F$_2$BO}

\begin{singlespace}
\begin{verbatim}
O    0.00000000            0.00000000            2.65260017
B    0.00000000            0.00000000            0.07681654
F    0.00000000            2.16433924           -1.13888019
F    0.00000000           -2.16433924           -1.13888019
 \end{verbatim}
\end{singlespace}

\subsubsection{F$_2$BS}

\begin{singlespace}
\begin{verbatim}
S    0.00000000            0.00000000            2.64960984
B    0.00000000            0.00000000           -0.74406239
F    0.00000000            2.14169276           -2.01390354
F    0.00000000           -2.14169276           -2.01390354
\end{verbatim}
\end{singlespace}

\subsubsection{H$_2$BO}

\begin{singlespace}
\begin{verbatim}
O    0.00000000            0.00000000            1.17360276
B    0.00000000            0.00000000           -1.27133435
H    0.00000000            1.98370787           -2.36904602
H    0.00000000           -1.98370787           -2.36904602
\end{verbatim}
\end{singlespace}

\subsubsection{HCO}

\begin{singlespace}
\begin{verbatim}
H    0.00000000           -2.55038496            1.39798104
C    0.00000000           -1.17300976           -0.19046167
O    0.00000000            1.04073447            0.05480615
\end{verbatim}
\end{singlespace}

\subsubsection{HOC}

\begin{singlespace}
\begin{verbatim}
H    0.00000000            1.82002973            1.50851586
O    0.00000000            0.96467865           -0.12887834
C    0.00000000           -1.43868535            0.04508983
 \end{verbatim}
\end{singlespace}

\subsubsection{H$_2$PO}

\begin{singlespace}
\begin{verbatim}
P    0.00000000            0.87766783           -0.10010856
O    0.00000000           -1.95912323            0.05701315
H    2.08101554            2.05955113            1.08591181
H   -2.08101554            2.05955113            1.08591181
\end{verbatim}
\end{singlespace}

\subsubsection{H$_2$PS}

\begin{singlespace}
\begin{verbatim}
P    0.00000000            1.81994516           -0.10769248
S    0.00000000           -1.93707861            0.02086846
H    2.03762554            2.75934101            1.32385757
H   -2.03762554            2.75934101            1.32385757
\end{verbatim}
\end{singlespace}

\subsubsection{NCO}

\begin{singlespace}
\begin{verbatim}
N    0.00000000            0.00000000           -2.39343558
C    0.00000000            0.00000000           -0.07238136
O    0.00000000            0.00000000            2.14968523
\end{verbatim}
\end{singlespace}

\subsubsection{NH$_2$}

\begin{singlespace}
\begin{verbatim}
N    0.00000000            0.00000000            0.15111603
H    0.00000000            1.51574744           -1.04982949
H    0.00000000           -1.51574744           -1.04982949
\end{verbatim}
\end{singlespace}

\subsubsection{Nitromethyl (CH$_2$-NO$_2$)}

\begin{singlespace}
\begin{verbatim}
C    0.00000000            0.00000000           -2.58417104
N    0.00000000            0.00000000            0.08692471
O    0.00000000           -2.06715629            1.15098225
O    0.00000000            2.06715629            1.15098225
H    0.00000000            1.81656349           -3.48616378
H    0.00000000           -1.81656349           -3.48616378
 \end{verbatim}
\end{singlespace}

\subsubsection{NO}

\begin{singlespace}
\begin{verbatim}
N    0.00000000            0.00000000           -1.15775086
O    0.00000000            0.00000000            1.01357658
\end{verbatim}
\end{singlespace}

\subsubsection{OH}

\begin{singlespace}
\begin{verbatim}
O    0.00000000            0.00000000           -0.10864763
H    0.00000000            0.00000000            1.72431679
\end{verbatim}
\end{singlespace}

\subsubsection{PH$_2$}

\begin{singlespace}
\begin{verbatim}
P    0.00000000            0.00000000            0.11427641
H    0.00000000            1.91899987           -1.75604411
H    0.00000000           -1.91899987           -1.75604411
\end{verbatim}
\end{singlespace}

\subsubsection{Vinyl (C$_2$H$_3$)}

\begin{singlespace}
\begin{verbatim}
C    0.00000000            1.16769663           -0.04303146
C    0.00000000           -1.29945364            0.15810072
H    0.00000000            2.38429609            1.59801822
H    0.00000000            2.08759130           -1.87998309
H    0.00000000           -2.90307925           -1.08814513
\end{verbatim}
\end{singlespace}

\bibliography{biblio-new}



\end{document} 

