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Context. The dusty winds of cool evolved stars are a major contributor of the newly synthesised material enriching the Galaxy and future generations of stars. However, the details of the physics and chemistry behind dust formation and wind launching have yet to be pinpointed. Recent spatially resolved observations show the importance of gaining a more comprehensive view of the circumstellar chemistry, but a comparative study of the intricate interplay between chemistry and physics is still difficult because observational details such as frequencies and angular resolutions are rarely comparable.Aims. Aiming to overcome these deficiencies, ATOMIUM is an ALMA Large Programme to study the physics and chemistry of the circumstellar envelopes of a diverse set of oxygen-rich evolved stars under homogeneous observing conditions at three angular resolutions between similar to 0.02''-1.4''. Here we summarize the molecular inventory of these sources, and the correlations between stellar parameters and molecular content. Methods. Seventeen oxygen-rich or S-type asymptotic giant branch (AGB) and red supergiant (RSG) stars have been observed in several tunings with ALMA Band 6, targeting a range of molecules to probe the circumstellar envelope and especially the chemistry of dust formation close to the star. We systematically assigned the molecular carriers of the spectral lines and measured their spectroscopic parameters and the angular extent of the emission of each line from integrated intensity maps. Results. Across the ATOMIUM sample, we detect 291 transitions of 24 different molecules and their isotopologues. This includes several first detections in oxygen-rich AGB/RSG stars: PO v = 1, SO2 v(1) = 1 and v(2) = 2, and several high energy H2O transitions. We also find several first detections in S-type AGB stars: vibrationally excited HCN v(2) = 2,3 and SiS v = 4,5,6, as well as first detections of the molecules SiC, AlCl, and AlF in W Aql. Overall, we find strong correlation

Context. The dusty winds of cool evolved stars are a major contributor of the newly synthesised material enriching the Galaxy and future generations of stars. However, the details of the physics and chemistry behind dust formation and wind launching have yet to be pinpointed. Recent spatially resolved observations show the importance of gaining a more comprehensive view of the circumstellar chemistry, but a comparative study of the intricate interplay between chemistry and physics is still difficult because observational details such as frequencies and angular resolutions are rarely comparable.Aims. Aiming to overcome these deficiencies, ATOMIUM is an ALMA Large Programme to study the physics and chemistry of the circumstellar envelopes of a diverse set of oxygen-rich evolved stars under homogeneous observing conditions at three angular resolutions between similar to 0.02''-1.4''. Here we summarize the molecular inventory of these sources, and the correlations between stellar parameters and molecular content. Methods. Seventeen oxygen-rich or S-type asymptotic giant branch (AGB) and red supergiant (RSG) stars have been observed in several tunings with ALMA Band 6, targeting a range of molecules to probe the circumstellar envelope and especially the chemistry of dust formation close to the star. We systematically assigned the molecular carriers of the spectral lines and measured their spectroscopic parameters and the angular extent of the emission of each line from integrated intensity maps. Results. Across the ATOMIUM sample, we detect 291 transitions of 24 different molecules and their isotopologues. This includes several first detections in oxygen-rich AGB/RSG stars: PO v = 1, SO2 v(1) = 1 and v(2) = 2, and several high energy H2O transitions. We also find several first detections in S-type AGB stars: vibrationally excited HCN v(2) = 2,3 and SiS v = 4,5,6, as well as first detections of the molecules SiC, AlCl, and AlF in W Aql. Overall, we find strong correlation

Context. The dusty winds of cool evolved stars are a major contributor of the newly synthesised material enriching the Galaxy and future generations of stars. However, the details of the physics and chemistry behind dust formation and wind launching have yet to be pinpointed. Recent spatially resolved observations show the importance of gaining a more comprehensive view of the circumstellar chemistry, but a comparative study of the intricate interplay between chemistry and physics is still difficult because observational details such as frequencies and angular resolutions are rarely comparable.Aims. Aiming to overcome these deficiencies, ATOMIUM is an ALMA Large Programme to study the physics and chemistry of the circumstellar envelopes of a diverse set of oxygen-rich evolved stars under homogeneous observing conditions at three angular resolutions between similar to 0.02''-1.4''. Here we summarize the molecular inventory of these sources, and the correlations between stellar parameters and molecular content. Methods. Seventeen oxygen-rich or S-type asymptotic giant branch (AGB) and red supergiant (RSG) stars have been observed in several tunings with ALMA Band 6, targeting a range of molecules to probe the circumstellar envelope and especially the chemistry of dust formation close to the star. We systematically assigned the molecular carriers of the spectral lines and measured their spectroscopic parameters and the angular extent of the emission of each line from integrated intensity maps. Results. Across the ATOMIUM sample, we detect 291 transitions of 24 different molecules and their isotopologues. This includes several first detections in oxygen-rich AGB/RSG stars: PO v = 1, SO2 v(1) = 1 and v(2) = 2, and several high energy H2O transitions. We also find several first detections in S-type AGB stars: vibrationally excited HCN v(2) = 2,3 and SiS v = 4,5,6, as well as first detections of the molecules SiC, AlCl, and AlF in W Aql. Overall, we find strong correlation

Context. The dusty winds of cool evolved stars are a major contributor of the newly synthesised material enriching the Galaxy and future generations of stars. However, the details of the physics and chemistry behind dust formation and wind launching have yet to be pinpointed. Recent spatially resolved observations show the importance of gaining a more comprehensive view of the circumstellar chemistry, but a comparative study of the intricate interplay between chemistry and physics is still difficult because observational details such as frequencies and angular resolutions are rarely comparable.Aims. Aiming to overcome these deficiencies, ATOMIUM is an ALMA Large Programme to study the physics and chemistry of the circumstellar envelopes of a diverse set of oxygen-rich evolved stars under homogeneous observing conditions at three angular resolutions between similar to 0.02''-1.4''. Here we summarize the molecular inventory of these sources, and the correlations between stellar parameters and molecular content. Methods. Seventeen oxygen-rich or S-type asymptotic giant branch (AGB) and red supergiant (RSG) stars have been observed in several tunings with ALMA Band 6, targeting a range of molecules to probe the circumstellar envelope and especially the chemistry of dust formation close to the star. We systematically assigned the molecular carriers of the spectral lines and measured their spectroscopic parameters and the angular extent of the emission of each line from integrated intensity maps. Results. Across the ATOMIUM sample, we detect 291 transitions of 24 different molecules and their isotopologues. This includes several first detections in oxygen-rich AGB/RSG stars: PO v = 1, SO2 v(1) = 1 and v(2) = 2, and several high energy H2O transitions. We also find several first detections in S-type AGB stars: vibrationally excited HCN v(2) = 2,3 and SiS v = 4,5,6, as well as first detections of the molecules SiC, AlCl, and AlF in W Aql. Overall, we find strong correlation

Context. The dusty winds of cool evolved stars are a major contributor of the newly synthesised material enriching the Galaxy and future generations of stars. However, the details of the physics and chemistry behind dust formation and wind launching have yet to be pinpointed. Recent spatially resolved observations show the importance of gaining a more comprehensive view of the circumstellar chemistry, but a comparative study of the intricate interplay between chemistry and physics is still difficult because observational details such as frequencies and angular resolutions are rarely comparable.Aims. Aiming to overcome these deficiencies, ATOMIUM is an ALMA Large Programme to study the physics and chemistry of the circumstellar envelopes of a diverse set of oxygen-rich evolved stars under homogeneous observing conditions at three angular resolutions between similar to 0.02''-1.4''. Here we summarize the molecular inventory of these sources, and the correlations between stellar parameters and molecular content. Methods. Seventeen oxygen-rich or S-type asymptotic giant branch (AGB) and red supergiant (RSG) stars have been observed in several tunings with ALMA Band 6, targeting a range of molecules to probe the circumstellar envelope and especially the chemistry of dust formation close to the star. We systematically assigned the molecular carriers of the spectral lines and measured their spectroscopic parameters and the angular extent of the emission of each line from integrated intensity maps. Results. Across the ATOMIUM sample, we detect 291 transitions of 24 different molecules and their isotopologues. This includes several first detections in oxygen-rich AGB/RSG stars: PO v = 1, SO2 v(1) = 1 and v(2) = 2, and several high energy H2O transitions. We also find several first detections in S-type AGB stars: vibrationally excited HCN v(2) = 2,3 and SiS v = 4,5,6, as well as first detections of the molecules SiC, AlCl, and AlF in W Aql. Overall, we find strong correlation

Context: Water (H2O) and the hydroxyl radical (OH) are major constituents of the envelope of O-rich late-type stars. Transitions involving energy levels that are rotationally or vibrationally highly excited (energies & GSIM;4000 K) have been observed in both H2O and OH. These and more recently discovered transitions can now be observed at a high sensitivity and angular resolution in the inner wind close to the stellar photosphere with the Atacama Large Millimeter/submillimeter Array (ALMA). Aims: Our goals are: (1) to identify and map the emission and absorption of H2O in several vibrational states, and of OH in Lambda-doubling transitions with similar excitation energies; and (2) to determine the physical conditions and kinematics in gas layers close to the extended atmosphere in a sample of asymptotic giant branch stars (AGBs) and red supergiants (RSGs). Methods: Spectra and maps of H2O and OH lines observed in a 27 GHz aggregated bandwidth and with an angular resolution of similar to 0."02-1."0 were obtained at two epochs with the main ALMA array. Additional observations with the Atacama Compact Array (ACA) were used to check for time variability of water transitions. Radiative transfer models of H2O were revisited to characterize masing conditions. Up-to-date chemical models were used for comparison with the observed OH/H2O abundance ratio. Results: Ten rotational transitions of H2O with excitation energies similar to 4000-9000 K were observed in vibrational states up to (& upsilon;(1),& upsilon;(2),& upsilon;(3)) = (0,1,1). All but one are new detections in space, and from these we have derived accurate rest frequencies. Hyperfine split Lambda-doubling transitions in & upsilon; = 0, J = 27/2 and 29/2 levels of the (2)& pi;(3/2) state, as well as J = 33/2 and 35/2 of the (2)& pi;(1/2) state of OH with excitation energies of similar to 4780-8900 K were also observed. Four of these transitions are new detections in space. Combining our

Context: Water (H2O) and the hydroxyl radical (OH) are major constituents of the envelope of O-rich late-type stars. Transitions involving energy levels that are rotationally or vibrationally highly excited (energies & GSIM;4000 K) have been observed in both H2O and OH. These and more recently discovered transitions can now be observed at a high sensitivity and angular resolution in the inner wind close to the stellar photosphere with the Atacama Large Millimeter/submillimeter Array (ALMA). Aims: Our goals are: (1) to identify and map the emission and absorption of H2O in several vibrational states, and of OH in Lambda-doubling transitions with similar excitation energies; and (2) to determine the physical conditions and kinematics in gas layers close to the extended atmosphere in a sample of asymptotic giant branch stars (AGBs) and red supergiants (RSGs). Methods: Spectra and maps of H2O and OH lines observed in a 27 GHz aggregated bandwidth and with an angular resolution of similar to 0."02-1."0 were obtained at two epochs with the main ALMA array. Additional observations with the Atacama Compact Array (ACA) were used to check for time variability of water transitions. Radiative transfer models of H2O were revisited to characterize masing conditions. Up-to-date chemical models were used for comparison with the observed OH/H2O abundance ratio. Results: Ten rotational transitions of H2O with excitation energies similar to 4000-9000 K were observed in vibrational states up to (& upsilon;(1),& upsilon;(2),& upsilon;(3)) = (0,1,1). All but one are new detections in space, and from these we have derived accurate rest frequencies. Hyperfine split Lambda-doubling transitions in & upsilon; = 0, J = 27/2 and 29/2 levels of the (2)& pi;(3/2) state, as well as J = 33/2 and 35/2 of the (2)& pi;(1/2) state of OH with excitation energies of similar to 4780-8900 K were also observed. Four of these transitions are new detections in space. Combining our

Context: Water (H2O) and the hydroxyl radical (OH) are major constituents of the envelope of O-rich late-type stars. Transitions involving energy levels that are rotationally or vibrationally highly excited (energies & GSIM;4000 K) have been observed in both H2O and OH. These and more recently discovered transitions can now be observed at a high sensitivity and angular resolution in the inner wind close to the stellar photosphere with the Atacama Large Millimeter/submillimeter Array (ALMA). Aims: Our goals are: (1) to identify and map the emission and absorption of H2O in several vibrational states, and of OH in Lambda-doubling transitions with similar excitation energies; and (2) to determine the physical conditions and kinematics in gas layers close to the extended atmosphere in a sample of asymptotic giant branch stars (AGBs) and red supergiants (RSGs). Methods: Spectra and maps of H2O and OH lines observed in a 27 GHz aggregated bandwidth and with an angular resolution of similar to 0."02-1."0 were obtained at two epochs with the main ALMA array. Additional observations with the Atacama Compact Array (ACA) were used to check for time variability of water transitions. Radiative transfer models of H2O were revisited to characterize masing conditions. Up-to-date chemical models were used for comparison with the observed OH/H2O abundance ratio. Results: Ten rotational transitions of H2O with excitation energies similar to 4000-9000 K were observed in vibrational states up to (& upsilon;(1),& upsilon;(2),& upsilon;(3)) = (0,1,1). All but one are new detections in space, and from these we have derived accurate rest frequencies. Hyperfine split Lambda-doubling transitions in & upsilon; = 0, J = 27/2 and 29/2 levels of the (2)& pi;(3/2) state, as well as J = 33/2 and 35/2 of the (2)& pi;(1/2) state of OH with excitation energies of similar to 4780-8900 K were also observed. Four of these transitions are new detections in space. Combining our

Context: Water (H2O) and the hydroxyl radical (OH) are major constituents of the envelope of O-rich late-type stars. Transitions involving energy levels that are rotationally or vibrationally highly excited (energies & GSIM;4000 K) have been observed in both H2O and OH. These and more recently discovered transitions can now be observed at a high sensitivity and angular resolution in the inner wind close to the stellar photosphere with the Atacama Large Millimeter/submillimeter Array (ALMA). Aims: Our goals are: (1) to identify and map the emission and absorption of H2O in several vibrational states, and of OH in Lambda-doubling transitions with similar excitation energies; and (2) to determine the physical conditions and kinematics in gas layers close to the extended atmosphere in a sample of asymptotic giant branch stars (AGBs) and red supergiants (RSGs). Methods: Spectra and maps of H2O and OH lines observed in a 27 GHz aggregated bandwidth and with an angular resolution of similar to 0."02-1."0 were obtained at two epochs with the main ALMA array. Additional observations with the Atacama Compact Array (ACA) were used to check for time variability of water transitions. Radiative transfer models of H2O were revisited to characterize masing conditions. Up-to-date chemical models were used for comparison with the observed OH/H2O abundance ratio. Results: Ten rotational transitions of H2O with excitation energies similar to 4000-9000 K were observed in vibrational states up to (& upsilon;(1),& upsilon;(2),& upsilon;(3)) = (0,1,1). All but one are new detections in space, and from these we have derived accurate rest frequencies. Hyperfine split Lambda-doubling transitions in & upsilon; = 0, J = 27/2 and 29/2 levels of the (2)& pi;(3/2) state, as well as J = 33/2 and 35/2 of the (2)& pi;(1/2) state of OH with excitation energies of similar to 4780-8900 K were also observed. Four of these transitions are new detections in space. Combining our

Context: Water (H2O) and the hydroxyl radical (OH) are major constituents of the envelope of O-rich late-type stars. Transitions involving energy levels that are rotationally or vibrationally highly excited (energies & GSIM;4000 K) have been observed in both H2O and OH. These and more recently discovered transitions can now be observed at a high sensitivity and angular resolution in the inner wind close to the stellar photosphere with the Atacama Large Millimeter/submillimeter Array (ALMA). Aims: Our goals are: (1) to identify and map the emission and absorption of H2O in several vibrational states, and of OH in Lambda-doubling transitions with similar excitation energies; and (2) to determine the physical conditions and kinematics in gas layers close to the extended atmosphere in a sample of asymptotic giant branch stars (AGBs) and red supergiants (RSGs). Methods: Spectra and maps of H2O and OH lines observed in a 27 GHz aggregated bandwidth and with an angular resolution of similar to 0."02-1."0 were obtained at two epochs with the main ALMA array. Additional observations with the Atacama Compact Array (ACA) were used to check for time variability of water transitions. Radiative transfer models of H2O were revisited to characterize masing conditions. Up-to-date chemical models were used for comparison with the observed OH/H2O abundance ratio. Results: Ten rotational transitions of H2O with excitation energies similar to 4000-9000 K were observed in vibrational states up to (& upsilon;(1),& upsilon;(2),& upsilon;(3)) = (0,1,1). All but one are new detections in space, and from these we have derived accurate rest frequencies. Hyperfine split Lambda-doubling transitions in & upsilon; = 0, J = 27/2 and 29/2 levels of the (2)& pi;(3/2) state, as well as J = 33/2 and 35/2 of the (2)& pi;(1/2) state of OH with excitation energies of similar to 4780-8900 K were also observed. Four of these transitions are new detections in space. Combining our